An optical humidity sensor based on CdTe nanocrystals modied porous silicon

Jing Hu
a
, Peng Wu
b
, Dongyan Deng
a
, Xiaoming Jiang
b
, Xiandeng Hou
a, b,
, Yi Lv
a,

a
College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China
b
Analytical & Testing Center, Sichuan University, Chengdu, Sichuan 610064, China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 24 September 2012
Accepted 5 October 2012
Available online 13 October 2012
Keywords:
CdTe nanocrystals
Porous silicon
Photoluminescence
Humidity sensor
In this work, mimicking the preparation of solid catalyst in heterogeneous catalysis, a composite for sensing was
constructed by the loading of mercaptopropionic acid (MPA) capped CdTe nanocrystals (NCs) on the porous sil-
icon surface (PSi/CdTe NCs composite). Since water vapor could effectively enhance the photoluminescence of
CdTe NCs onPSi, the as-prepared composite was engineeredinto anoptical humidity sensor. Time-resolved uo-
rescence measurements showed that the loading of CdTe NCs onto PSi and post-photoradiation led to the gen-
eration of surface traps on the surface of CdTe NCs. Upon adsorption of water molecules, the amounts of
surface traps were effectively decreased, thus providing PL improvement. By employing the proper modication
strategy, this humidity sensor achieved the convenience and repeatability in construction of the sensing layer,
good sensitivity and stability. This humidity sensor also shows good selectivity against common volatile organic
compounds. For absolute humidity, the linear range was 240 g/mL in N
2
or 1.326.7 g/mL in dry air, both
with a limit of detection of 0.3 g/mL. For relative humidity (RH), the linear range could be from 12% to 93% at
20 C. This sensor was also successfully applied in the RH determination of real air samples, with results well
agreed with a commercial hygrometer.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Semiconductor nanocrystals (NCs), or quantum dots (QDs) with
their excellent optical properties, have beenextensively employedas op-
tical labels and probes for biosensing [14], and optical probes for metal
ions [59]. These sensing events are typically carried out in solution
media, while for gas sensing, solid state NCs are often used and embed-
ded into polymer matrix [1013]. Semiconductor NCs based gas-sensing
materials mainly feature the following characteristics: (i) sensitive and
rapid response to gases, due to the large surface-to-atom ratio and the
high susceptibility of NCs to the change of surface environment; and
(ii) the enhanced selectivity or the expandeddetectionrange of analytes,
due to the versatile and matured NCs surface functionalization strategies
[2,14,15]. However, the utilization of NCs for gas sensing is at the pri-
mary stage, mainly because semiconductor NCs are usually capped
with a dense monolayer of organic ligands which prevents the effec-
tive interaction between gas molecules and the surface of NCs [10].
Aiming at improving the interaction, a simple and effective strategy
of photoactivation was therefore proposed to make the ligands
monolayer of NCs readily permeable to gas molecules [10]. Another
strategy is the surface-modication of NCs for specic analytes,
with improved sensitivity and selectivity [12].
In addition to the improvement of NCs themselves, the careful de-
sign of sensing interface between the NCs and gases is also of vital im-
portance to the sensing performance. In most cases, NCs are
encapsulated into poly(methyl methacrylate) (PMMA) or poly(dimeth-
ylsiloxane) (PDMS). Subsequently, the mixture is cast on Si or glass sub-
strates. However, the use of PMMA or PDMS actually generated another
barrier between gas molecules and the surface of NCs, reducing the
sensing sensitivity and prolonging the recovery time. In heterogeneous
catalysis, for the preparationof solidcatalysts, the active components for
catalysis are often dispersed on a suitable supporter. Such design pro-
vides the following advantages: (i) improving the effective interaction
of catalyst with reactants and accelerating the adsorptiondesorption
process; and (ii) enhancing the catalysis performance through regularly
arranging the active components on the support with uniformmorphol-
ogy [1618]. The construction of a solid catalyst-like NC-based gas sen-
sor may benet enough from the existed knowledge of heterogeneous
catalysis and lead to improved gas sensor performance. However, ele-
gant selection of the supporter for the NCs and subsequent modication
strategy is obviously the rst to be considered.
Porous silicon (PSi) is a favorable candidate as the supporter. Since
accidentally discovered in the mid 1950s [19], PSi has been extensively
explored as chemical/bio-sensors, supporter for chemical applications
as well as biochemical reactions and proteomics, due to distinct proper-
ties of its unique surface [20]. PSi is rstly characterized of the large sur-
face area with controllable and ordered pores, consequently as an
Microchemical Journal 108 (2013) 100105
Corresponding author at: College of Chemistry, Sichuan University, Chengdu, Sichuan
610064, China. Tel.: +86 28 85470818; fax: +86 28 85415695.
Corresponding author.
E-mail addresses: houxd@scu.edu.cn (X. Hou), lvy@scu.edu.cn (Y. Lv).
0026-265X/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.microc.2012.10.005
Contents lists available at SciVerse ScienceDirect
Microchemical Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ mi cr oc
excellent supporter. Examples include desorptionionization on PSi
surface for mass spectrometry [21], heterogeneous support for catalytic
growth of highly uniform carbon nanotubes [22], porosied enzyme
microreactors with increased activity [23] etc. The versatile and conve-
nient surface chemistry is another attracting advantage, since PSi sur-
face could achieve any surface termination upon demand, by a variety
of wet chemical functionalization techniques [2426]. Typically, Sailor
et al [27] introduced a series of surface modication strategies for load-
ing of analyte-specic receptors and achieved sensitive protein or DNA
detection. However, to our knowledge, the use of PSi as a support for
loading of semiconductor NCs for development of sensing devices has
never reported before. Inthis work, we employed a proper modication
strategy to decorate mercaptopropionic acid capped CdTe NCs on the
surface of PSi to engineer an optical humidity sensor.
Humidity is one of the most common physical quantities and its
measurement is of signicant importance for a wealth of areas, includ-
ing air conditioning, process control and product store in industry as
well as agriculture [28]. Early established hygrometers are conned by
the limitations such as slowresponse, inherent non-linearity, and oper-
ation place limit [29]. Electronic humidity sensors [30], on the other
hand, suffer from the temperature dependence and the susceptibility
to some chemical species. The optical humidity sensor in this work
was based on the direct response to the humidity via the PL enhance-
ment due to the passivation of NCs surface by adsorbed water mole-
cules. Beneting from the utilization of sensing composite (PSi/CdTe
NCs composite), this humidity sensor achieves high sensitivity and
good recovery. Together with the good selectivity, this sensor is a prom-
ising alternative for humidity measurement.
2. Experimental section
2.1. Reagents and materials
Reagents used in this work were of at least analytical grade.
CdCl
2
2.5H
2
O, KBH
4
(Kelong Reagent Factory, Chengdu, China), and Te
powder (Sinopharm Chemical Reagent Co. Ltd) were used to prepare
CdTe NCs, and 3-mercaptopropionic acid (MPA) (Alading Reagent Co.,
Shanghai, China) was used as the capping agent. P-type, b100>,
boron-doped Si wafers (812 cm) were etched by using a mixture of
ethanol and HF (40 wt.%) to form the PSi layers. (3-aminopropyl)
triethoxysilane (APTES, bought from Alfa Aesar China (Tianjin) Co.,
Ltd.), 1-ethyl-3-(3-dimethyllaminopropyl) carbodiimide (EDCHCl) and
1-hydroxypyrrolidine-2,5-dione (NHS), both bought from Alading Re-
agent Co., were used for the modication of PSi. N
2
(99.999%) and med-
ical O
2
(99.5%) were used as the carrier gas because the concentration of
water in them were very low (b3 ppmv). Dry air was prepared by
mixing N
2
and O
2
under proper ratio.
2.2. Synthesis of CdTe NCs
Synthesis of CdTe NCs was based on a previous publication but with
small modications [31]. Briey, 1.9 mM KBH
4
and 0.8 mM Te powder
reacted in 10 mL oxygen free water under 60 C for 60 min to form
KHTe. The reaction was protected by N
2
stream, and nally a purplish
red solution was obtained. CdCl
2
2.5H
2
O (1 mM) and MPA (1.3 mM)
were dissolved in 150 mL of water. The mixture was adjusted to
pH 10.5 with 1 M NaOH and deoxygenized with N
2
stream for
20 min. Subsequently, 2 mL of freshly prepared KHTe was quickly
injected into 150 mL of Cd
2+
precursor solution under vigorous stirring
for 20 min, and thenthe resultant solutionwas reuxed for 40 min. The
obtained CdTe NCs solution was precipitated with n-propanol, and then
centrifugated (11,000 rpm) to remove the supernatant. The puried
CdTe NCs were redispersed in double distilled water (DDW). The size
and concentration of the CdTe NCs were estimated based on Peng's
method [32].
2.3. Preparation of PSi
The siliconwafers (11 cm
2
) were etchedat a constant current den-
sity of 40 mA/cm
2
in a mixture of HF (40 wt.%): ethanol (v/v=1:1) for
30 min. The formed PSi layers (0.80.8 cm) were then rinsed with eth-
anol, 1 M KOH (to remove the SiO
x
), DDW, ethanol and n-pentane in
order. Finally, the PSi layers were dried under N
2
stream. It is worth-
while to note that the PSi layer could be reproducibly prepared by this
electrochemical method. However, be careful when using HF, and the
experiment should be carried out under the hood.
2.4. Modication of PSi
The schematic procedure was shown in Fig. 1, and the method was
named as electrostatic assembly. Briey, the PSi layer was rstly func-
tionalized with APTES according to a previous method [33]. Then, the
APTES-PSi layer was immersed in diluted HCl (concentrated HCl/
DDW=1:9) for 20 s to protonate the amino group and dried under N
2
stream [34]. Finally, 50 L 0.025 mM CdTe NCs solution was dripped
on the layer and dried in air under room temperature. It was found
that CdTe NCs solution could easily disperse across the protonated
silanized PSi layer. The other three modication methods are for com-
parison with electrostatic assembly, and the details are presented in
the Supporting information.
2.5. Characterization of CdTe NCs and sensing layer
The UVvisible absorptionspectrumof CdTe NCs was obtainedusing
a Shimadzu 1750 UVvis spectrophotometer, and the spectra of the
UVvis absorption and the PL emission were shown in Fig. 2a. The com-
parison of PL spectra of 0.025 mMCdTe NCs solution and PSi/CdTe NCs
composite was shown in Fig. 2b. The morphologies of the sensing layer
were characterized using a JSM-5900LV scanning electron microscope
(SEM) operated at an accelerating voltage of 20 kV.
2.6. Sensor fabrication
The PSi/CdTe NCs layer was put into a Teon sensing cell with a gas
inlet and an outlet, and a piece of quartz window covered on the cell.
The schematic illustration of humidity sensing by the present sensor
was shown in Fig. 3a. The sensing cell was mounted on a solid sample
holder and the PL signals were recorded with a Hitachi F-7000 uores-
cence spectrometer (Hitachi Company, Japan). The excitation was set at
350 nm throughout the work, with the excitation and emission slit
width both of 5 nm. The photoluminescence spectra of CdTe NCs and
PSi/CdTe NCs layer were recorded in the range of 450650 nm. For hu-
midity measurement, the programof time scan was employed, with ex-
citation at 350 nmand emission at the PL peak of the sensing layer. The
peak area was used for quantication throughout the work.
2.7. Absolute humidity measurement
The absolute humidity measurement was carried out in high purity
N
2
(as a typical inert gas) and dry air. For typical measurement, proper
amount of water was directly injected into the 30 mL heated bottle (at a
constant temperature of 150 C). After totally vaporized (20 s), the car-
rier gas with a owrate of 400 (N
2
) or 200 (dry air)mL/min ushed the
water vapor into the sensing cell for detection.
2.8. Relative humidity calibration
Six over-saturation solutions of specic salts, i.e. LiCl, MgCl
2
,
Mg(NO
3
)
2
, NaCl, KCl and KNO
3
were put in six 100 mL conical asks, re-
spectively. Six plastic syringes containing 60 ml clean air were mounted
on those asks and sealed at 20 C for at least 24 h. After that, the rela-
tive humidity (RH) values of the air in the corresponding syringes were
101 J. Hu et al. / Microchemical Journal 108 (2013) 100105
12, 33, 55, 75.7, 85 and 93%, respectively [35]. For RHcalibration, 10 mL
air withthe specic RHvalue was injected and ushed by the dry air at a
speed of 100 mL/min to reach the sensing cell for determination.
2.9. Air samples
Four air samples (20 C) were collected froma bathroom, an ofce
building, an instrument room and a laboratory for organic synthesis
respectively. For each measurement, 10 mL sample was injected and
ushed by the dry air also with a speed of 100 mL/min to reach the
sensing cell. A commercial hygrometer (Beijing Yaguang Instrument
Corporation, supervised by the National Research Center for Certied
Reference Materials) was used for validation.
3. Results and discussion
3.1. Design and characterization of the PSi/CdTe NCs composite
The physical/chemical properties of PSi surface andCdTe NCs togeth-
er with the interaction between them dictate the convenience and re-
peatability in construction of the sensing layer. The native PSi was
hydrophobic with ordered pores of 13 m spreading over the etched
region of Si wafer (Fig. 4a), while CdTe NCs used in this work were
water soluble. Therefore, in order to render the PSi surface hydrophilic,
amino groups were mounted onto the PSi surface via silanized with
APTES and thenprotonated (Fig. 1). Consequently, CdTe NCs were easily
spread over the PSi region, due to the electrostatic interaction between
protonated amino groups on PSi and negatively charged MPA of CdTe
NCs. Branch-like strips of NCs covered the surface of PSi pore skeleton
densely (Fig. 4b), indicating the facile construction of sensing layer.
Three other CdTe NCs loading methods were alsoinvestigated, including
amide bonding modication, physical adsorption and gel coating (see
the Supporting information). However, possibly due to the poor com-
patibility of these methods, PSi surface morphology characterizations
showed that CdTe NCs in these cases could not spread as evenly as
that of electrostatic assembly (see Fig. S2). Accordingly, electrostatic as-
sembly was employed for loading of CdTe NCs onto the surface of PSi.
Interestingly and importantly, post-photoradiation of PSi/CdTe NCs
composite could re-regulate the loaded CdTe NCs on the surface of PSi,
resulting in further dispersing of CdTe NCs over the ordered pores of
PSi. As shown in Fig. 4b and c, after the as-prepared PSi/CdTe NCs com-
posite (sealed in N
2
) was subjected to photoradiation for 10 min, the
loadedCdTe NCs over the surface of PSi changedfromrandomscattering
to the well-dispersing along the PSi pore skeleton. Obviously, electro-
static assembly of CdTe NCs with PSi plus post-photoradiation provide
a barrier-less sensing layer for water vapor to well contact with CdTe
NCs, which is advantageous over the conventional PMMA or PDMS en-
capsulating strategies. The reason for such photo re-arrangement was
not very clear at the present stage. However, the weak assembly of
CdTe NCs onthe surface of PSi throughelectrostatic interactionprovided
further probability for such re-arrangement.
3.2. Brief discussion of sensing mechanism
The change in the surface state of NCs would signicantly affect their
PL properties [36], which is the fundamental for the development of the
NCs-based gas sensors [10]. Time-resolved PL experiments showed that
the lifetime of CdTe NCs deposited on PSi was greatly shortened com-
pared with that of CdTe NCs solution (Fig. 5), indicating that surface de-
fects were created after CdTe NCs were transferred from the solution to
the solid state. Furthermore, post-photoradiation of the sensing layer
(PSi/CdTe NCs composite) not only provides increased contact area be-
tween analyte and CdTe NCs, but also creates defects on the surface of
CdTe NCs [37]. It has beenreportedthat the electron-donating molecules
(Lewis basis) adsorbed on the surface of CdSe NCs are prone to passivate
their surface traps, resulting in PL enhancement [38,39]. Based on the
similarity of CdTe and CdSe NCs, we thus speculated that PL enhance-
ment caused by gaseous water (a well-known Lewis basis) in this
work could also be attributed to the elimination of surface traps. Upon
the adsorption of water molecules, the lifetime of CdTe NCs deposited
Fig. 1. Schematic diagram of silanization of PSi and electrostatic assembly.
Fig. 2. (a) Photoluminescence emissionandUVabsorptionspectra of MPA-CdTe NCs, and(b) photoluminescence emissionspectra of MPA-CdTe NCs of 0.025 mMandPSi/CdTe NCs composite.
102 J. Hu et al. / Microchemical Journal 108 (2013) 100105
on PSi was obviously increased (still much shorter than that of solution),
which proved the passivation of partial surface defects by water mole-
cules and consequently, enhanced PL.
3.3. The sensitivity and stability of the sensing layer
Surface chemistry has been reported to have a pronounced effect
on analyte response in PSi based sensors, in terms of sensitivity, selec-
tivity and stability [40]. Sensitivity investigations showed that elec-
trostatic assembly gave the best sensitivity (Fig. 6), which could be
ascribed to the ever-increased contact area between analyte with
CdTe NCs. Note that the poor sensitivity of surface by NCs gel coating
(similar with PMMA or PDMS encapsulating strategies), which was
attributed to the block from the dense siloxane network around
CdTe NCs. This further proves that the barrier-less sensing interface
is a better choice.
The stability of the sensing layer was investigated in a period of
22 days. As shown in Fig. 6, the stability of PSi/CdTe NCs was the best
compared with those by other three modication methods, probably be-
cause of the unique environment around the NCs and morphology by
this electrostatic assembly. The stability of the sensing layer was accept-
able for relative long-time use, since the exposure to air during humidity
sensing only caused weak oxidationand PL decrease, and it was sealed in
N
2
when not used. Note that there was an increase in response on the
5th day, possibly due to the increase of surface traps on the CdTe NCs
during the 5-day aging process. In this case, the CdTe NCs would be
even more accessible to water molecules, thus the PL enhancement
was enlarged. In contrast, the sensing layer provided by physical adsorp-
tion exhibited an obviously decreased sensing response. In such physical
adsorption, the spreading of CdTe NCs over PSi was orderless and
couldn't spreadorientally over the orderedpores of PSi. Thus PSi couldn't
provide a protective environment for CdTe NCs and over oxidation of the
CdTe NCs was generated during the preparation and utilization.
Fig. 3. (a) Schematic illustration of humidity sensing by the present sensor, and (b) the responses of PSi/CdTe NCs composite to 13.3 g/mL water vapor.
Fig. 4. SEM images of (a) porous silicon; (b) PSi/CdTe NCs composite; and (c) PSi/CdTe
NCs composite after photoradiation.
Fig. 5. PL decay curves of CdTe NCs solution, PSi/CdTe NCs and PSi/CdTe NCs with the
adsorption of water molecules.
103 J. Hu et al. / Microchemical Journal 108 (2013) 100105
3.4. Effect of carrier ow rate on recovery and sensitivity
Previous research results showed that the PL enhancement by the
adsorption of water was a semi-reversible behavior due to the strong
bonding of water on NCs surface [38,39]. Therefore, the present sensor
was used under ow mode: the carrier gas brought the gaseous water
into the sensing cell for detection and ushed it away from the sensing
layer. Together with the small sampling amount, this sampling mode
could effectively reduce the strong bonding effect of water molecule,
beneting the recovery, repeatability and the lifetime of this sensor.
As demonstrated in Fig. 3b, the reproducible PL enhancement with re-
covery time about 2 min was achieved. For the absolute humidity de-
termination in high purity N
2
atmosphere, the signal decreased as the
increase of ow rate in the range of 160 to 600 mL min
1
(Fig. S3).
However, low ow rate would be detrimental to sensor recovery.
Therefore, 400 mL/min was nally selected for use in consideration of
both sensitivity and recovery. In the case of humidity determination
in air, the high ow rate of air would bring more O
2
each time, which
quenched the PL effectively to depress the PL enhancement by water
molecules. A low ow rate of 200 mL/min was therefore employed for
the determination of the absolute humidity in air, while an even
lower one of 100 mL/minwas used for the relative humidity calibration.
3.5. Selectivity of the sensor
The selectivity of the present humidity sensor was evaluated using a
series of common volatile organic compounds (VOCs) of 26.4 g/mL, in-
cluding alcohol (methanol, ethanol and n-propanol), acetone, ethyl ace-
tate, n-hexane, cyclohexane, chloralkanes (dichloromethane, chloroform
and carbon tetrachloride), acetonitrile, tert-butylamine and NH
3
. Of
these VOCs, no detectable or very weak (for NH
3
) signals were obtained,
indicating good selectivity of the proposed humidity sensor. The reason
for the selectivity was not very clear at the present stage. Possibly, the
physical/chemical property of the PSi (support), the capping agent and
the surrounding environment for NCs, contributed greatly to the selec-
tivity of this sensor. The present sensor was not suitable for atmosphere
with NH
3
of high concentration, but could be widely applied in common
cases.
3.6. Analytical gures of merit
The linear dynamic range of the PL enhancement versus water con-
centration was found to be 240 g/mL in high purity N
2
and 1.3
26.7 g/mL indry air, both witha limit of detection of 0.3 g/mL. Typical
calibration curves using the optimized parameters could be character-
ized by the following calibration functions: y=29.6x+9.3 (R=
0.996) in N
2
, and y=41.3x+10.2 (R=0.998) in dry air, where y is
the improved PL intensity, x is the concentration of water, and R is the
regression coefcient. Relative standard deviations (RSDs, n=3) were
0.7%, 0.6%, and 1.9% for 2 g/mL, 13.3 g/mL, and 40 g/mL water in
N
2
; and 4.7%, 1.9%, and 0.4% for 1.3 g/mL, 13.3 g/mL, and 26.7 g/
mL water in dry air, respectively. For relative humidity, six relative hu-
midity concentrations of 12%, 33%, 55%, 75.7%, 85% and 93% were tested,
andthe linear regressionequationis described by y=250.6x+8.6 (R=
0.998). RSDs (n=3) were 4.2%, 2.4%, 1.5% for 33% RH, 75.7% RH and
93%RH, respectively. The goodanalytical performance indicates the pro-
posed sensor is suitable for humidity measurement either in inert gas or
in the air.
3.7. Relative humidity determination of air samples
The proposed PSi/CdTe NCs composite sensor was applied to the rel-
ative humidity determination of real air samples, including three sam-
ples with different RH range in common places, and a sample from an
organic synthesis laboratory in which contains some ethyl acetate,
dichloromethane and n-hexane. As shown in Table 1, the determined
RHvalues agreed well with that measured by a commercial hygrometer,
even for the VOCs-containing sample. These results demonstrated the
potential of this sensor in real world sample determination.
4. Conclusion
An optical humidity sensor using the CdTe NCs modied porous sil-
icon composite was developed. Porous silicon was demonstrated as a
favorable supporting material for loading of semiconductor NCs. More
importantly, the CdTe NCs could be regulated along the PSi pore skele-
ton under UV irradiation to form reliable and well-performed sensing
layers. Furthermore, its various surface chemistry couldprovide a versa-
tile platformavailable for different ligand-capped NCs or functionalized
NCs for target analyte. For the modication strategy, electrostatic as-
sembly shows the best compatibility with the surface of porous silicon,
thus forming the most uniform, sensitive and stable sensing layers. The
owsampling mode is also important for good recovery and stability of
the present sensor. This optical humidity sensor, which features direct
detection of water vapor with high sensitivity and good selectivity,
should be promising in on-site monitoring humidity of environment,
warehouse areas and more.
Acknowledgment
The authors gratefully acknowledge the nancial support for this
project from the National Natural Science Foundation of China (no.
20835003). The authors also thank the Analytical & Testing Center
of Sichuan University for obtaining SEM data, and Professor HUANG
Chengzhi in Southwest University for his assistance in carrying out
uorescence time-resolved experiments.
Fig. 6. Sensingsensitivity andstabilitycomparisonwithother three modicationmethods.
Water vapor concentration, 13.3 g/mL for PSi/CdTe NCs composite, the surface by amide
bonding modication, and the surface by physical adsorption; 33.3 g/mL for the surface
by gel coating. Air ow rate, 200 mL/min. The PL quenching response from the surface
by gel coating was called for further investigation.
Table 1
Analytical results of relative humidity determination of air samples.
Sample Found by this method
(average, n=3)/%RH
Found by a
commercial hygrometer
(average, n=3)/%RH
Air in a bathroom 79.70.6 81.00.8
Air in an ofce building 63.81.4 62.01.0
Air in an instrument room 50.60.6 50.01.2
Air in an organic synthesis
laboratory
49.20.8 50.00.9
104 J. Hu et al. / Microchemical Journal 108 (2013) 100105
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.microc.2012.10.005.
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