Sensors and Actuators B 189 (2013) 146156

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Sensors and Actuators B: Chemical

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

Silicon resonant nanopillar sensors for airborne titanium dioxide engineered

nanoparticle mass detection
Hutomo Suryo Wasisto a, , Stephan Merzsch a , Andrej Stranz a , Andreas Waag a , Erik Uhde b ,
Tunga Salthammer b , Erwin Peiner a
a
b

Institute of Semiconductor Technology (IHT), Braunschweig University of Technology, Hans-Sommer Str. 66, D-38106 Braunschweig, Germany
Material Analysis and Indoor Chemistry (MAIC), Fraunhofer-Wilhelm-Klauditz-Institut (WKI), Bienroder Weg 54E, D-38108 Braunschweig, Germany

a r t i c l e

i n f o

Article history:
Received 17 September 2012
Received in revised form 12 February 2013
Accepted 13 February 2013
Available online 21 February 2013
Keywords:
Silicon nanopillars
ICP cryogenic dry etching
Airborne engineered nanoparticles
Mass sensitivity

a b s t r a c t
This work demonstrates mass measurement of airborne titanium dioxide (TiO2 ) engineered nanoparticles
(ENPs) using silicon resonant nanopillar sensors by monitoring resonant frequency shifts induced by the
mass of trapped ENPs. Inductively coupled plasma (ICP) cryogenic dry etching and thermal oxidation have
been used in the sensor fabrication. A piezo shear actuator and an electrostatic precipitator are utilized
to excite the nanopillars in resonant mode and collect the owing TiO2 ENPs, respectively. By using the
fundamental bending frequency, the sensor can achieve a mass sensitivity of 7.22 Hz/fg, which enables
its application to a nanobalance to detect airborne ENPs in the femtogram mass range. Two methods
of ENP removals (i.e., polydimethylsiloxane (PDMS) and ultrasonic cleanings) have also been performed
to remove the adhered ENPs, thus efciently extending the operating life of the sensor. This developed
sensor is targeted to be implemented as a handheld ENP monitoring device at workplaces.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Nanotechnology is currently well-known in society owing to
its widespread use in modern applications [1]. Commercial products used in daily life (e.g., cosmetics, pharmaceuticals, medical
devices, food packaging, odor-resistant textiles, and household
appliances) are manufactured involving engineered nanoparticles
(ENPs). Despite the ENP benets, there is an increasing attention
to the potential risk of the released ENPs on human health and the
environment. ENPs can enter the human body mostly by inhalation,
resulting in pulmonary inammation [2,3]. The inhaled airborne
ENPs are deposited efciently in all regions of the respiratory tract
depending on their sizes, shapes, densities, and surface properties.
In experimental conditions, such nuisance types of ENPs (e.g., titanium dioxide (TiO2 ) and carbon black) are found to be harmful
to the lung [2]. Moreover, from rodent cancer studies, TiO2 particles have been evaluated as possibly carcinogenic to humans by
the International Agency for Research on Cancer (IARC) [4]. Therefore, many researches to date have focused on the assessment of
inhalation exposures to TiO2 ENPs at the workplace [24].
In the most epidemiological studies, the effect of ENPs in the
respiratory tract is suggested to the inhaled mass. The World
Health Organization also has dened guidelines for PM10 and PM2.5

Corresponding author. Tel.: +49 531 391 3776; fax: +49 531 391 5844.
E-mail address: h.wasisto@tu-bs.de (H.S. Wasisto).
0925-4005/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.02.053

in ambient air using mass-related units [5]. Thus, direct mass

sensing of airborne TiO2 ENPs is very helpful for the assessment
of personal and location-dependent monitoring at the workplace
and the indoor environment. To assist on this evaluation, some
micro/nanoelectromechanical system (MEMS/NEMS) based resonant mass sensors have been used to determine mass concentration
and size distribution of aerosol particles [68]. Such resonators can
be of a low-cost batch fabricated as individual devices or arrays.
Compared with the conventional resonant mass sensors (e.g., surface acoustic wave (SAW) and quartz crystal microbalance (QCM))
[9,10], MEMS/NEMS-based resonators can provide orders of magnitude higher mass sensitivity and resolution due to their much
smaller sizes. Mass sensitivity as high as 1.5 kHz/pg was measured
for the I-shaped bulk acoustic resonators (IBARs) with detected particles of 200 nm in diameter [6]. Another resonant mass sensor
fabricated as piezoresistive cantilever with an integrated Wheatstone bridge showed feasibility to assess exposure to very small
engineered carbon ENPs of typically 20 nm in diameter with a
mass resolution of 4.8 pg [7]. However, further miniaturization of
the resonator dimensions to achieve higher mass sensitivity is still a
necessity. Therefore, NEMS-based silicon nanopillars or nanowires
are attractive to assist the development of miniaturized sensors.
Nanopillar resonators can offer the potentials for both resonant
operation under workplace conditions and the largest surface area
[11,12]. These benets can extensively broaden the applications of
silicon nanopillar arrays, which have previously been employed in
many emerging applications, including thermoelectric generators

H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

147

[13,14], templates for GaN growth in metal-organic vapor-phase

epitaxial (MOVPE) [15], biomedical sensors [16], chemical sensors
[17], and eld effect transistors [18]. To realize those nanostructures in semiconductors, a sequence of patterning and etching processes is usually required, except for bottom-growth techniques.
In this work, a fabrication and a characterization of silicon
nanopillar resonators, which are capable of detecting airborne TiO2
ENP mass in the femtograms regime, are described. Nanopillars are
fabricated using inductively coupled plasma (ICP) cryogenic dry
etching followed by multiple thermal oxidation and oxide stripping. Instead of using thermophoretic force, the collection of ENPs is
performed using electrostatic force in a precipitator operated without a corona discharger. Results of detecting airborne TiO2 ENPs in
pillar arrays are presented and analyzed. Two simple but highly
efcient cleaning methods of polluted nanopillars have also been
tested to remove the adhered ENPs, hence prolonging the use of
sensors.
2. Silicon resonant nanopillar sensors
2.1. Fabrication of silicon nanopillar resonators
In the fabrication of the nanopillars or nanowires, a deep reactive ion etching (DRIE) with a high aspect-ratio is one of the most
important processing steps besides patterning (i.e., lithography).
Generally, DRIE can be classied into two main process technologies, i.e., the Bosch etching process and the cryogenic dry etching
process [1922]. Some researchers have demonstrated the feasibility of using the Bosch etching process to realize nanowire structures
[19,20]. The persistent drawbacks of this method are the requirement of two alternating gases (i.e., C4 F8 and SF6 for passivation
and etching, respectively), process complexity (i.e., synchronization of the passivation and the etching cycles), unclean process
(i.e., the passivation layer covering the reactor walls during the
passivation cycle), and the scalloping effect (i.e., scallop-shaped
sidewalls). Considerable effort was made in the Bosch recipe
to reduce the scallop size of the etched structure sidewalls by
adding an argon/oxygen plasma pulse in between the passivation and etching steps as well as a short oxygen clean step at
the end of each cycle. However, it was found to be still difcult
to achieve smooth and vertical sidewalls for very deep structures
[19].
In contrast to the Bosch etching process, the cryogenic dry etching process can produce high-aspect-ratio nanostructures as well
as maintain smooth and vertical etched structure sidewalls [21].
Cryogenic dry etching offers a clean process due to gaseous etch
products (i.e., SF6 and O2 ) and passivation layers that are fully
desorbed during the heating up from the etch temperature (i.e.,
between 75 C and 140 C) to room temperature. Moreover,
using high-density plasma, from which the ions are extracted at low
ion energy, and working at high vacuum can remarkably improve
the performance of cryogenic dry etching. Compared with wet etching using alkaline solutions, ICP cryogenic dry etching in silicon is an
anisotropic process that is independent of crystallographic directions. Furthermore, the possibility of using a photoresist instead of
thermal silicon dioxide (SiO2 ) or other hard materials as an etching mask is also benecial for this etching method [13]. Therefore,
the ICP cryogenic dry etching process is selected to be used in this
work.
Fig. 1 shows the process ow for the silicon nanopillar fabrication. The detailed explanation can be described as follows:
(a) To start the fabrication process, a silicon wafer of 300 m thick
was covered by photoresist (AZ 726 MIF) at a spinning speed of
3000 rpm and for a duration of 35 s. Thus, a photoresist mask of

Fig. 1. Schematics of process ow for the fabrication of silicon nanopillars illustrating: (a) photoresist coating, (b) UV-lithography, (c) ICP cryogenic dry etching, (d)
photoresist cleaning, (e) thermal oxidation, and (f) HF etching.

(b)
(c)

(d)

(e)

(f)

0.6 m was successfully deposited on the whole surface area of

the silicon wafer.
The photoresist mask was then patterned using UV lithography,
resulting in a round-shaped structure.
By using an SI 500 C cryogenic dry etcher (Sentech Instruments),
the patterned silicon sample was etched within 230 s at 75 C
and a reactor pressure of 1.5 Pa in SF6 /O2 plasma. During the
ICP cryogenic etching process, the photoresist mask was found
to be stable for at least 0.4 hours. From the experiments, the
etch rate of silicon using the ICP cryogenic dry etching can
reach up to 4 m/min. In comparison, typical etch rates of
the Bosch process and anisotropic wet etching using 44% KOH
solution at 82 C are 2.3 m/min [20] and 0.7 m/min [13],
respectively.
Here, after ICP cryogenic dry etching, the photoresist layer was
washed off in a solution mixture of hydrogen peroxide (H2 O2 ,
30%) and concentrated sulfuric acid (H2 SO4 , 96%) within ve
minutes inside a quartz glass placed on a heating plate with
temperature of 90 C. In this step, the analyzed pillars have an
aspect ratio of >10 and a diameter of 3.5 m.
To further reduce the diameter of the pillars, a thermal oxidation of the dry-etched pillars was performed followed by oxide
stripping. This method was used because thermal oxidation is
considered to be a highly reproducible process to generate a
conformal sacricial layer on a 3-D silicon structure under uniform consumption of silicon, which can then be removed at
a very high selectivity to the residual silicon [13]. After three
times oxidation and oxide stripping, the reduction of the pillar
diameter was obtained (i.e., from 2840 nm to 650 nm).
Subsequently, the SiO2 layer formed in thermal oxidation was
etched and stripped off using buffered hydrouoric acid (HF,
67%) solution inside a small glass within 10 min, which was
followed by DI water rinsing. Finally, after the sample had been
dried, the silicon nanopillar arrays were successfully achieved.

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Fig. 3. (a) Schematic and (b) photograph of the resonant frequency measurement
setup of silicon nanopillar resonator.

By assuming that I and  are constant along the length of cantilevered beam, the resonant frequencies fn of oscillation for a
cantilevered beam can be calculated as
fn =

n2
2h2

EI
h

(2)

where n is 1.875, 4.694, 7.854, (n 0.5), for n = 1, 2, 3, 4. The

integer subscripts n correspond to the resonant modes.
In case of a hollow cylindrical-shaped beam, such as a multiwalled nanotube (MWNT), of inner diameter di and outer diameter
do , Eq. (2) can be rewritten as
n2
fn =
8h2
Fig. 2. SEM images of silicon pillars after (a) ICP cryogenic dry etching and (b) third
thermal oxidation and oxide stripping in buffered HF.

 do4 + di4
and

h =

In order to calculate the resonant frequency of a nanopillar, the

silicon nanopillar can be modeled by treating the nanopillar as a
cantilevered beam of the length h. According to the EulerBernoulli
beam theory, the transverse vibration of a cantilevered beam is
given as [23]
(1)

where y, E, I, and h are the bending deection of the beam, the

Youngs modulus of elasticity, the area moment of inertia, and the
material density per unit length calculated by multiplying the density of beam  by its cross-sectional area A, respectively.

(3)


(4)

64

 do2 di2

(5)

are used as the substitutions. However, for a solid nanopillar as

produced in this work, it does not have an inner diameter (di = 0).
Therefore, Eq. (3) can be simplied further as
n2
fn =
do
8h2

E


(6)

In case of the fundamental exural vibration (1 = 1.875) of a

uniform circular cross-section nanopillar, the resonant frequency
f1 can then be theoretically obtained as [24]
0.439 do
f1 =
 h2

2.2. Characterization of silicon nanopillar resonators

EI 4 y
2 y
+
=0
h x4
t 2


E 2
d + di2
 o

where
I=

Using this process sequence, the generated silicon pillars have

aspect ratios of more than 60 and diameters down to 650 nm.
Fig. 2(a) shows a typical pillar array after ICP cryogenic dry
etching. The effect of the etching process to the bottom pillar clamped end is obvious for the outermost row of the pillar
arrays, whereas the sidewalls of pillar arrays inside the rim are
found to be smooth and vertical. The area density of the pillars is
1.6 106 mm2 . The smaller diameter of pillars achieved after thermal oxidation and oxide stripping processes is shown in Fig. 2(b).
By reducing the pillar diameter, an increase of displacement and
decrease of pillar mass can be expected, which is expected to
cause an increase of mass sensitivity and quality factor of the
device.

E


(7)

With the silicon density  of 2.33 g/cm3 and Youngs modulus of

elasticity of 169 GPa, the fundamental resonant frequency f1 of the
employed silicon nanopillar (do = 650 nm, h = 40 m) is calculated
to be 483.97 kHz.
To validate the theoretical analysis of the resonant frequency,
the fabricated nanopillars are then characterized in a resonant
frequency measurement. Fig. 3(a) shows the schematic of the
experimental setup for excitation of silicon nanopillars in resonance. Initially, a sample comprising silicon nanopillars was
mounted onto a piezo shear actuator using a conductive carbon
tape for adhesion. The piezoactuator can produce vibration in
lateral direction. Subsequently, the mount was placed into a scanning electron microscope (SEM) chamber which was evacuated

H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

149

Fig. 6. Airborne titanium dioxide (TiO2 ) ENP sampling setup.

Fig. 4. SEM images of a tested silicon nanopillar in its (a) stationary and (b) fundamental resonant mode.

(2 107 kPa). To have a connection to the outer side of the chamber, the elastic cable wires of the piezoactuator were then plugged
into a small metal plate, which was used as a mediator to the electronic measurement equipment. By applying an AC sinus voltage
Upp of 10 V to the piezoactuator, the nanopillars could be driven
in mechanical vibration. A waveform generator (HP 33120A) was
used as an AC voltage source with the frequency sweep range up
to 500 kHz. All aspects of the experiments were directly observed
and imaged with an SEM as depicted in Fig. 3(b).
In order to obtain a quantitative analysis, seven nanopillars
located close to each other on the substrate have been measured in
resonance (Fig. 4). The maximum deection of the pillar is determined from the top view as shown in the inset of Fig. 4(b). The
measured resonant frequencies of those bare silicon nanopillars
range from 434.63 0.02 kHz to 458.21 0.37 kHz, with an average
value of 446.58 8.92 kHz as plotted in Fig. 5. Despite an agreement with the theory, the resonant frequencies of the nanopillars
measured in the experiment are systematically lower than those
calculated using Eq. (7). These differences can be attributed to
the shapes and dimensions of the nanopillars, which are not ideal
cylindrical-shaped structures. Affected by the thermal oxidation
process, the pillars rather exhibit a slight tendency toward conical
shapes. However, these experimental results are still acceptable
because the deviations of the seven measured pillars are found
to be less than 11%, thus verifying the fabrication quality of the
nanopillar resonators. Moreover, the quality factors (Q-factors) of

Fig. 5. Comparison of resonant frequencies of silicon nanopillars yielded by theory

and measurement.

the investigated nanopillars are in the range of 12001700. The

values of the measured Q-factors are determined by tting the
obtained nanopillar deection curves using a simple harmonic
oscillator (SHO) t function as previously used for the cantilever
responses with the given SHO amplitude response AP of [8]:
AP = Aoff +




A0
1

f2
f2

2

f
QfP

2

(8)

where Aoff is the offset amplitude, A0 is the nanopillar deection

amplitude at zero frequency, fP is the measured resonant frequency
and f is the swept frequency in Hz.
3. Airborne titanium dioxide-based engineered
nanoparticle sampling
3.1. Experimental details
To test the functioning of the silicon resonant nanopillars used
as an airborne ENP mass detector, an assessment using TiO2 -based
ENPs was performed in a test chamber under a typical workplace
conditions (V = 1 m3 , T = 23 C, rH = 30%, p = 1 atm) as depicted in
Fig. 6. A fast mobility particle sizer (FMPS, TSI 3091) with a time resolution of 1 s was utilized for in situ monitoring the particle number
concentration and size distribution of ENPs. The working principle of FMPS is based on the electrical aerosol spectrometer (EAS)
[25]. The incoming particles are rstly charged in a unipolar corona
charger. They are then classied and measured with an array of 22
electrometers where each channel corresponds to a dened electrical mobility bandwidth. Therefore, by knowing the particle charge
levels, the measured currents of the electrometers can be extracted
into particle number size distributions (5.6562.3 nm). Adding all
the numbers of the measured particles will yield a total concentration of the owing aerosols. In this experiment, test aerosols
with a total measured concentration of 8000 particle/cm3 were
generated by nebulizing a suspension of TiO2 nanoparticles in
water/ethanol using a constant output atomizer (TSI 3076), followed by a dryer.
The aerosols typically consisted of positively charged, negatively charged, and neutral ENPs. To collect the airborne ENPs onto
the nanopillars, a nanometer aerosol sampler (NAS, TSI 3089) was
used as an electrostatic precipitator (ESP), which consists principally of a grounded cylindrical sampling case with an electrode at
the bottom of the case. The ENP collection process is illustrated
in Fig. 7(a). During a 30-min ENP sampling, a high negative voltage of 9.5 kV was set to the electrode, which was connected
with the bulk contact of the silicon nanopillars to generate electric elds over the sensor. The NAS was then run at a xed ow

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Fig. 7. Schematics of (a) a nanometer aerosol sampler comprising Si nanopillars connected to a negative bias voltage and (b) the force balance on an incoming ENP in the
area above the nanopillar surface.

rate. A constant ow of particle-laden air of 1 l/min was conducted through the small inlet of the sampler (inlet = 3.5 mm). An
enhanced ENP sampling on the pillar can be expected due to the
electric eld between the grounded sealing case and the electrode
that attracts positively charged ENPs and polarizes the uncharged
fraction. In the nonuniform eld at the bottom electrode, ENPs then
experience an attractive force (i.e., mainly electrostatic force). This
force pulls ENPs into the higher electric eld gradient region on
the nanopillars. The rest of TiO2 aerosol, including the negatively
charged ENPs, which are denitely repelled from the substrate,
will ow out through the outlet located on the bottom rim of the
NAS.
The more specic process of the aerosol ENP collection in ESP
has been explained by Krinke et al., who have modeled the ENP
trajectory as a force balance on a single ENP approaching the substrate [26]. Basically, the ENP collection processes on a nanopillar
substrate can be divided into two cases. The rst case is the situation where the location of the ENP is far away from the pillar,
hence interactions between the incoming ENP and the nanopillar substrate surface do not occur. In this case, the ENPs exhibit
the convective and Brownian motions, because the ENP surfaces
have collided with gas molecules creating a random force Fstochastic .
Moreover, when a voltage is applied to the NAS electrode, the
electrostatic force or Coulomb force (FCoulomb ) also takes place. In
contrast, at the second case, the interaction of the incoming ENP
with the nanopillar substrate surface starts to inuence the ENP
motion because the ENPs are sufciently close to the nanopillar
substrate. Thus, the image and van der Waals (vdW) forces between
the ENP and the nanopillar substrate surfaces (Fimage PS and FvdW PS )
arise in this situation. As soon as some ENPs have been stuck on the
nanopillar substrate, the incoming airborne ENP will most likely be
deposited on the other already trapped particles. In this case, image
and van der Waals forces caused by interactions of the incoming

ENP with another ENP (Fimage PP and FvdW PP ) arise. Additionally, a

dipole force, Fdipole , can be considered to take place due to the inhomogeneous eld around the deposited ENPs. Lastly, the external
force acting on an ENP Fext can be described by neglecting gravity
as [26]
Fext = FCoulomb + Fimage

PS

+ Fimage

PP

+ Fdipole + FvdW

PS

+ FvdW

PP

(9)
The illustration of the force balance on an incoming ENP in the
area of the nanopillar substrate surface is depicted in Fig. 7(b). The
boundary between the rst and second processes is about 200 nm
depending on the particle diameter as previously investigated by
Krinke et al. and Tsai et al. [26,27].
Additionally, in this experiment, the total concentration of the
generated TiO2 ENPs monitored by FMPS can be further analyzed
for determining the particle size distribution during sampling. By
assuming the ENPs are spherically shaped, the total of owing ENP
mass can be estimated, with a single TiO2 particle mass mENP of
mENP =

 3
dENP ENP
6

(10)

where dENP is the particle diameter, and ENP is the TiO2 density. By knowing the incoming aerosol ow rate of 1000 cm3 /min
and TiO2 density of 4.23 g/cm3 , the total mass and number of
the owing airborne ENPs through the NAS can be determined
as mENPs = 2189.77 ng and NENPs = 2.44 108 particles, respectively.
Fig. 8 shows the size distributions of the number and mass concentrations of owing TiO2 ENPs during the assessment. Herein, it
is obvious that the ENPs mostly had diameters of 125 nm with
the number and mass concentrations of 2.87 107 particles and
121.53 ng, respectively.

H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

151

Fig. 8. (a) Total mass and (b) number of airborne TiO2 ENPs acting upon silicon
nanopillar arrays during 30-min sampling as measured by FMPS (TSI 3091). The
mass is calculated from the number of TiO2 ENPs assuming a spherical shape.
Fig. 9. SEM image of the silicon nanopillars polluted by TiO2 ENPs.

3.2. Sampling results and analysis

As expected from the assessment, during a 30-min TiO2 ENP
sampling, Si nanopillars have successfully collected an amount of
positively charged airborne ENPs by using the electrostatic precipitation method. Those ENPs are adhered on the whole pillar surfaces
as shown in Fig. 9. However, it is apparent that the number of total
ENPs stuck on each pillar is not the same. Instead of being stuck
uniformly on the whole surface of the substrate, the TiO2 ENPs prefer to be deposited on the pillars, especially on the upper part of the
pillar. They are arranged in ENP agglomerates. This result coincides
with the model of ENP attraction due to the electrical eld and eld
gradient, which are higher in these regions than in the bottom at
substrate areas (Fig. 7(b)). Only a few ENPs are deposited on the
lower part of the pillar because there is less gas ow (drag force)
near the substrate due to friction at the surface. After an ENP has
been trapped to the pillar surface, it adopts the electrical potential
of the pillar. Once the potential has shifted, the already-deposited
ENP will act as an additional point on the surface altering the local
electric eld. As a result, the succeeding positively charged airborne ENPs prefer to land and stick with the earlier-deposited ENPs,
which end up in a dendrite shape of ENP agglomerates. Bayer et al.
have also showed that the pillar length and the distance between
pillars have signicant inuences on the ENP distribution [28]. By

increasing the pillar length, the ENPs that land on the upper part of
the pillar will be more in number. It is due to a longer distance that
the ENPs have to go along the pillars as they approach the substrate
surface, whereas by increasing the distance between the pillars, the
ENPs spread over the pillar length will be less in number. It can be
understood that the more space the ENPs have for moving around
(i.e., governed by Brownian motion), the more likely they are to
land on the substrate surface or the lower part of the pillar.
In order to determine the total number and mass of ENPs on each
pillar, frequency shifts induced by added ENP mass are investigated
for the seven selected pillars investigated prior to ENP deposition. The polluted Si nanopillars were mounted into the SEM and
excited in resonance showing that the adhered TiO2 ENPs were
moving together with the pillars during vibration, which brought
the resonant frequencies of the pillar into a lower value (Fig. 10).
The adhesion of the ENPs to the pillar surface was high enough to
keep the ENPs sticking on the pillar. Fig. 11 depicts the measured
shift of the fundamental exural resonant frequency induced by the
total TiO2 ENPs mass adhered to pillar P1. The distribution of the
resonant frequency shifts for seven investigated pillars is shown
in Fig. 12. As expected, pillars with more collected ENPs reveals
a larger resonant frequency shift fPj with a maximum value of
fP7 = 14.39 0.02 kHz observed with pillar P7 and a minimum
shift of fP2 = 2.16 0.37 kHz exhibited by pillar P2. SEM images

Fig. 10. SEM images of a polluted silicon nanopillar during vibration. The adhered TiO2 ENPs move together with the pillar.

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Moreover, the sensitivity of a mass-loaded nanopillar SPj is dened

as
SPj =

Fig. 11. Measured shift of the fundamental exural resonant frequency induced by
the total TiO2 ENPs mass adhered to nanopillar P1 within 30 min.

Fig. 12. Measured resonant frequency shifts of seven polluted nanopillars.

depicted in Fig. 13 conrm this result qualitatively, i.e., it can be

seen that the pillar P7 has collected considerably more TiO2 ENPs
than pillar P2. The attached ENPs agglomerate rather than form a
layer on the pillars. Therefore, we can assume that the spring constant of the pillars does not change and the ENP mass load mPj in
terms of the frequency shift fPj can be calculated as
mPj =

2 mPj fPj
fPj

(11)

where mPj and fPj are the mass and the resonant frequency of the
bare silicon pillar Pj, respectively. The integer subscript j corresponds to the number of the investigated pillars (j = 1, 2, . . ., 7).

fPj
mPj

(12)

For pillar P1, with a weight mP1 = 30.9 pg, an unloaded

resonant frequency fP1 = 452.33 0.01 kHz, and a resonant frequency shift fP1 = 5.81 0.01 kHz, a total deposited ENP mass
mP1 = 794.47 1.51 fg can be calculated. Table 1 shows the experimental results of all pillars in terms of the resonant frequency
shifts, the mass and number of the deposited ENPs, and the mass
sensitivity, respectively. It can be seen that the mass sensitivities
of all pillars are nearly the same, conrming the uniformity of the
fabricated Si nanopillars. By averaging the obtained values, a mass
sensitivity SP17 of 7.22 0.14 Hz/fg is then yielded from the experiment. This Si nanopillar has improved the mass sensitivity of our
cantilever detector by a factor of 0.7 million compared with the
former design [8]. Furthermore, with the frequency resolution of
0.01 kHz of the present measurement, a mass resolution of 1.5 fg
can be estimated corresponding to a lower detection limit of a
single ENP with a diameter of 125 nm. A comparison of the mass
sensitivity and resolution of the Si NEMS pillar with those of different technologies such as SAWs [9], QCMs [10], IBARs [6], and
Si MEMS cantilevers [8] is shown in Table 2. From this evaluation,
the Si nanopillars show better sensitivities when compared with
the other technologies due to their much smaller sizes. SAWs and
Si MEMS cantilever resonators exhibit minimum detectable mass
limits in the picogram range. The QCM resonators are even less sensitive having a mass resolution in the nanogram range as reported
by Lee et al. [10], whereas Si NEMS pillars can achieve a mass resolution in orders of magnitude higher than the other mass sensors
(i.e., in the femtogram range).
As supposed to trap all owing ENPs, the evaluation of the airborne ENP sampling efciency ENPs needs to be conducted. The
sampling efciency ENPs is given by the relation
ENPs =

mENPs
100%
mENPs

(13)

where mENPs and mENPs are the masses of the total owing and
deposited TiO2 ENPs, respectively. In this test, the pillar array covers an area of 10 mm2 . At a pitch between the pillars of 10 m,
this corresponds to a total number of 100,701 pillars. Knowing
the average deposited ENP mass per pillar of 761.16 fg, the total
mass of collected ENPs can be calculated as 76.65 ng, assuming the
uniform deposition of the ENPs on all pillars. Based on Eq. (13), a
sampling efciency of 3.5% was revealed with the mass of total

Fig. 13. SEM images of polluted pillars P2 and P7. Pillar P7 exhibits much more collected TiO2 ENPs supporting the higher observed resonant frequency shift compared to P2.

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153

Table 1
Experimental data for seven observed Si nanopillar sensors.
Si Pillar

Resonant frequency shift (kHz)

P1
P2
P3
P4
P5
P6
P7

5.81
2.16
3.22
4.32
5.21
3.24
14.39

0.01
0.37
0.02
0.12
0.02
0.03
0.02

Mass of the deposited ENPs (fg)

794.47
291.58
441.85
591.05
741.20
460.36
2007.64

1.51
49.47
2.60
17.07
2.93
3.66
3.16

Number of the deposited ENPs

(ENP = 125 nm) (#)
184
67
102
137
171
106
464

1
11
1
4
1
1
1

Mass sensitivity (Hz/fg)

7.31
7.41
7.28
7.30
7.03
7.05
7.17

0.01
1.26
0.04
0.21
0.03
0.06
0.01

owing airborne ENPs mENPs = 2189.77 ng. One reason for this considerable loss of sampling efciency was the charge distribution in
the aerosol (i.e., the ENPs were not completely positively charged,
but negatively charged and uncharged ENPs also occurred). Those
negatively charged ENPs were denitely repelled from the pillar, whereas uncharged and insufciently polarized ENPs were
expected to pass through without being deposited on the nanopillar
sample. Moreover, electric eld intensities might have been insufcient. It becomes a concern that the current ENP sampling efciency
needs to be improved to enhance the sensing performance. Thus,
optimization of both the electrostatic ENP sampler [29] and the
nanopillar design are considered in the further development of
airborne ENP sensing system.

3.3. Nanoparticle removal

Fig. 14. Schematics of a soft stamp creation of PDMS for Si pillar surface cleaning
illustrating: (a) PDMS dropping on the polluted pillar surfaces, (b) thermal curing,
(c) particle removal, and (d) cleaned pillar surfaces.

After being exposed to the aerosol, it becomes important to have

a method to make the nanopillar sensor reusable. Consequently,
the attached ENPs have to be removed from the nanopillar surfaces.

Fig. 15. SEM images of silicon pillar arrays (a) before and (b) after PDMS cleaning. The ENPs are clearly removed from the surfaces of the pillars substrate.

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H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

Table 2
Comparison of the mass sensitivity and resolution of the Si NEMS pillar with those of different technologies.
Sensor type

Mass sensitivity

Mass resolution

Reference

Surface acoustic wave (SAW)

Quartz crystal microbalance (QCM)
I-shaped bulk acoustic resonator (IBAR)
Silicon MEMS cantilever
Silicon NEMS pillar

900 Hz/ng
0.2 Hz/ng
1500 kHz/ng
10 Hz/ng
7220 kHz/ng

3000 fg
5.6 107 fg
10 fg
1000 fg
1.5 fg

Bowers et al. [9]

Lee et al. [10]
Hajjam et al. [6]
Wasisto et al. [8]
This work

Thus, two cleaning methods (i.e., polydimethylsiloxane (PDMS) and

ultrasonic cleanings) were tested in the lab to accomplish it. The
surface conditions of the sample before and after the ENP-removal
treatment were then analyzed using SEM.
In the rst ENP-removal method, PDMS, a well-known silicone
in the eld of soft lithography, with the type of Sylgard 184 from
Dow Corning was used [30,31]. A sequence of polluted nanopillars
treated in a PDMS cleaning is shown in Fig. 14. The detailed ENPremoval process can be described as follows:
(a) Some droplets of liquid PDMS were deposited on an ENPpolluted sample surface. To assure that the PDMS really
attached and covered the entire surface and ENPs, local bubbles
in and below the PDMS layer had to be removed.
(b) Subsequently, the PDMS-coated nanopillars were put on a heating plate at a temperature of 200 C within 1 h to make the PDMS
hard.
(c) After baking, the hardened PDMS, together with the enclosed
ENPs, was separated from the nanopillar sample.
(d) Finally, since the cohesion strength of the silicone mold was
much stronger than the binding forces between ENPs and the
sample surface, it resulted in a clean surface of the nanopillar
sample after PDMS detachment.
The PDMS-cleaning process was successfully implemented to
the polluted Si pillars (do = 15 m, h = 10 m). As can be seen in
Fig. 15, almost all ENPs were removed from the pillars. The downy
shape of the ENP agglomerates advanced the encapsulation by
PDMS. The resulting enormous footprint between ENPs and PDMS
simplies the cleaning. The efciency for this Si pillar cleaning is
estimated to be at least 99%. Nevertheless, this method was hardly
performed for thinner (do < 800 nm) and longer (h > 30 m) pillar
structures due to their fragility. This can be considered as a drawback of this PDMS cleaning.

Fig. 16. Schematic of ultrasonic cleaning for removing the attached ENPs from pillar
surfaces.

In the second ENP-removal method, an ultrasonic cleaner was

used [32,33]. This method is relatively simple, but efcient to
remove ENPs from the nanopillar substrate surface. The polluted
Au-coated Si pillars (h = 40 m, do = 650 nm) were used as a sample for testing in a clean room. The cleaning was started by placing
the sample in the glass with acetone solution or deionized water
(DI water) inside. The glass was then put into an ultrasonic bath
containing DI water. During the high-pressure stage of the cleaning process, the formed bubbles or cavitations imploded, releasing
enormous amounts of energy attacking every surface. Hence after
one to two minutes, the deposited ENPs were detached from the
pillar surface (Fig. 16). Correspondingly, using a Bandelin Sonorex
Ultrasonic bath TK 52 (f = 35 kHz), it was found that the ENPs were
removed from the nanopillar surface at efciencies of 9799%. The
pillar surface conditions before and after the ultrasonic cleaning
process are depicted in Fig. 17(a) and (b), respectively. It is obvious
that the imploding cavitations during ultrasonic cleaning have carried the ENPs away from the pillar surfaces. However, there were
a few pillars that fell down to the substrates because they accidentally hit the glass wall during the removal process. Therefore, the

Fig. 17. SEM images of Au-coated silicon nanopillars (a) before and (b) after ultrasonic cleaning. The ENPs are clearly detached from the surfaces of the pillars.

H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

sample has to be treated more carefully. Duration and power of the

ultrasonic cleaner also need to be optimized to avoid the broken
pillars. Regardless of sample handling and treatment, these two
cleaning processes (i.e., PDMS and ultrasonic cleanings) appeared
to be successful for efciently extending the operating life of the
sensors depending on the pillar dimensions.
4. Conclusion
Silicon nanopillar arrays have been developed and used as resonators for measuring the mass of airborne TiO2 ENPs in the
femtogram scale. Nanopillar arrays were fabricated utilizing ICP
cryogenic dry etching and thermal oxidation followed by oxide
stripping. The agreement between predicted values for both calculated and measured resonant frequencies has conrmed the
fabrication quality and validated its use in further sensor optimization. The distribution and settlement of airborne ENPs have been
observed, which mostly occurred in the upper part of the nanopillars. Recycling of the sensors was successfully tested with PDMS
and ultrasonic cleaning methods. To be implemented as a handheld
device and operated in a real workplace condition, a miniaturized
electrostatic aerosol sampler and a self-sensing cantilever-based
resonator will be integrated and coupled with the nanopillars.

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

Acknowledgements
The authors would like to thank I. Kirsch, S. Wientzek, J. Arens
and D. Rmmler for their valuable technical assistances. This work
is performed in the collaborative project NanoExpo funded by the
German Federal Ministry of Education and Research (BMBF) within
the cluster NanoCare under no. 03X0098A.

[22]

[23]
[24]

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Biographies
Hutomo Suryo Wasisto received the Bachelor of Engineering degree in electrical
engineering from the Gadjah Mada University, Indonesia and the Master of Engineering degree in semiconductor engineering from the Asia University, Taiwan, in

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H.S. Wasisto et al. / Sensors and Actuators B 189 (2013) 146156

2008 and 2010, respectively. Currently, he is working toward the Ph.D. degree at the
Institute of Semiconductor Technology (IHT), TU Braunschweig, Germany, where
he is involved in the eld of semiconductor sensors and M/NEMS-based technology
for portable aerosol nanoparticle sensing devices. He has published more than 25
papers in international scientic journals and conference proceedings. He has also
been the recipient of the second best young scientist poster award at the 26th European Conference on Solid-State Transducers (Eurosensors 2012) held in Krakow,
Poland.
Stephan Merzsch received the Diplomingenieur (Dipl.-Ing.) degree in electrical engineering from the Braunschweig University of Technology, Braunschweig,
Germany in 2008. Since 2008, he is a Ph.D. student at the Institute of Semiconductor
Technology (IHT), TU Braunschweig, Germany. Currently, he is working on semiconductor sensors, microsystems technology, and nanoimprint techniques for airborne
nanoparticle sensors.
Andrej Stranz received the Diplomingenieur (Dipl.-Ing.) degree in electrical engineering from the Braunschweig University of Technology, Braunschweig, Germany
in 2006. He is currently a Ph.D. student at the Institute of Semiconductor Technology
(IHT), TU Braunschweig, Germany. His research interests include characterization of
thermal and electrical properties of new nano-structured thermoelectric materials
and the corresponding packaging technologies.
Andreas Waag received his diploma as well as Ph.D. degree in physics from the
University of Wrzburg, Germany, in 1985 and 1990. In 1996, he got the Gaede
Award of the German Vacuum Society for the development of novel IIVI materials
for blue-green laser diodes. Since 2003, he is a full professor at TU Braunschweig,
University of Technology and head of the Institute of Semiconductor Technology

(IHT), with activities in the eld of oxides and nitrides for optoelectronics, as well
as sensor and joining technology.
Erik Uhde received his diploma in chemistry (1994) and later his Ph.D. (physical
chemistry, 1998) from the Braunschweig University of Technology, Germany. In
1995, he started as a project manager at Fraunhofer WKI. Since 2001, he is the
deputy head of the department of Material Analysis and Indoor Chemistry, which
specializes in the characterization of gaseous and solid air pollutants indoors. He is
a member of national and international standardization groups in the eld of indoor
air quality.
Tunga Salthammer received a diploma degree in chemistry (1986) and a Dr.rer.nat.
in Physical Chemistry (1990) from the Braunschweig University of Technology,
Germany. He joined the Fraunhofer WKI in 1990, where he currently serves as
deputy director and head of the Department of Material Analysis and Indoor Chemistry. Since 2007 he has been an adjunct professor at the Queensland University of
Technology (QUT) in Brisbane, Australia. He is a member of the Indoor Air Hygiene
Commission of the German Federal Environment Agency.
Erwin Peiner received the Diplom-Physiker and Ph.D. degrees from the University
of Bonn, Germany in 1985 and 1988, respectively. In 2000 he received the venia
legendi for semiconductor technology from the Faculty of Mechanical and Electrical
Engineering of the TU Braunschweig. Currently, he is the leader of the semiconductor sensors and metrology group at the Institute of Semiconductor Technology (IHT)
of the TU Braunschweig. He has published more than 150 papers in international
journals and conference proceedings. He is the project coordinator of the collaborative project NanoExpo funded by the German Federal Ministry of Education and
Research (BMBF).