VOL. 3, NO.

10, OCTOBER 2019 2000504

Sensor materials

Orthogonal Sensors for the Trace Detection of Explosives

Peter P. Ricci1,2 , Andrew S. Rossi1,2 , and Otto J. Gregory1.2
1 Sensors and Surface Technology Partnership, University of Rhode Island, Kingston, RI 02881 USA
2 Department of Chemical Engineering, University of Rhode Island, Kingston, RI 02881 USA

Manuscript received June 11, 2019; revised July 9, 2019 and August 2, 2019; accepted September 21, 2019. Date of publication October 2, 2019; date of
current version October 15, 2019.

Abstract—There is a growing need for an electronic trace detection system that can continuously monitor explosives at
trace levels in the vapor phase. Triacetone triperoxide (TATP) is a common explosive used by terrorists as the initiator
or the energetic material in improvised explosive devices. TATP still goes largely undetected in many densely populated
public venues. Currently, no detection system exists that is capable of continuously monitoring TATP, as well as nitrogen-
based explosives such as 2,4-dinitrotoluene. We have demonstrated a thermodynamic sensor platform employing thin
film microheaters and metal oxide catalysts that can detect TATP and 2,4-DNT at the parts per billion (ppb) level.
The microheaters and catalysts were deposited onto ultrathin alumina ceramic substrates, which are responsible for
extraordinary sensitivity. Recently, we have added a conductometric sensor platform to this thermodynamic platform to
form an orthogonal sensor capable of interrogating the same catalyst using two different modalities. The orthogonal sensor
probes the same catalyst using a thermodynamic protocol, as well as a conductometric protocol where electrical resistivity
changes in the catalyst are measured as a function of analyte exposure. The advantages of this added orthogonality in
terms of mitigating false-positives and negatives are described within.

Index Terms—Sensor materials, catalysts, explosive vapor detection, orthogonality, resistivity.

I. INTRODUCTION [3]; however, because of the temperature dependence on separation

Improvised explosive devices (IEDs) are commonly used by ter-
rorist organizations to threaten and/or cause harm to the general pub-
lic. The IEDs frequently employ triacetone triperoxide (TATP) as
either the detonator or the energetic material itself. This is largely
due to the ease of fabrication and availability of its precursors. In
just the past three years, terrorist attacks on airports, concerts, and
even churches have employed IEDs using TATP. Both TATP and trini-
trotoluene (TNT) decompose and sublime from solid to vapor. The
presence of these explosives in the vapor phase provides the ability to
establish a detection protocol for vapors. Due to the low vapor pressure
of TNT, detection relies on the decomposition product of TNT; i.e.,
2,4-DNT, which has a significantly higher vapor pressure, making it
easier to detect.
Many platforms exist that are capable of detecting either solid ex-
plosive or explosive vapor at very low concentrations. But each of
these platforms has their own drawbacks in terms of detecting ex-
plosives quickly and effectively. For example, Mullen et al. [2] used
single photon laser ionization techniques in conjunction with time of
flight mass spectrometry to detect certain explosives at the parts per
billion (ppb) level in the vapor phase. However, this technique requires
significant power and complex equipment that would not be feasible
from a maintenance and portability viewpoint.
Fluorescence and gas chromatography techniques have been inves-
tigated in an attempt to identify TATP in the vapor. However, the TATP
does not exhibit fluorescence [1], and gas chromatography is difficult
to perform due to the tendency for TATP to decompose under moderate
heating [1]. It is possible to detect TATP by gas chromatography/mass
spectrometry and mass chromatography/tandem mass spectrometry
Corresponding author: Peter P. Ricci (e-mail: pricci3@my.uri.edu).
Associate Editor: J. Gardner.
Digital Object Identifier 10.1109/LSENS.2019.2944587
time, this process is too time consuming to be implemented in fast
moving security venues.
Ion mobility spectrometry (IMS) is a detection method that is ex-
tremely fast (about 3 s to positively identify explosives); however, the
IMS is marginal for detecting explosives in the vapor [4]–[6]. Liquid
chromatography [7], as well as dielectric barrier discharge ionization-
mass spectrometry [8], require solids or solutionized explosives, and
therefore, would be ineffective for detection unless swabbed for
explosives.
Other researchers have been able to successfully detect explosive
vapors using conductometric techniques whereby electrical resistance
changes in a metal oxide are measured as the explosive vapor interacts
with it. However, conductometric sensors typically exhibit poor selec-
tivity, which has stimulated researchers to look for different strategies
to overcome this drawback. To our knowledge, a sensor that probes
the same metal oxide catalyst using a thermodynamic protocol as well
as conductometric protocol has never been demonstrated. The results
presented within suggest that our conductometric platform provides a
built-in redundancy that insures a much lower rate of false positives
than other techniques previously reported [9], [10]. Our orthogonal
sensor platform first described by Mallin [11] is unique in that both
sensing modalities (conductometric and thermodynamic) are function-
alized on the same substrate and the same catalyst is simultaneously
interrogated using these two independent modalities.
As previously described by Rossi et al. [12], our thermodynamic
sensor relies on two separate microheaters: one coated with a metal
oxide catalyst and an uncoated reference microheater. The reference
is used to distinguish between heat effects that arise from catalyst-
analyte interactions and those due to hydrodynamic effects such as
sensable heat effects. By subtracting the reference signal from the
catalyst-coated signal, the resulting difference is the heat effect due to
catalytic decomposition. The thermodynamic platform relies on oxi-
dation/reduction reactions on the catalyst surface after decomposition

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2000504
Fig. 1. Photograph of an orthogonal sensor (a) and top view of an
orthogonal sensor (b). A cutaway view (c) of an orthogonal sensor
shows the various layers comprising the sensor: A metal oxide (catalyst)
layer (1), nickel interdigitated electrodes (2), alumina coatings (3) and
(4), nickel microheater (5), and alumina substrate (6).
of the explosive molecule. These reactions can be exothermic or en-
dothermic depending on the temperature of the sensor, the analyte,
and the metal oxide catalyst. When the explosive molecule interacts
with the heated catalyst, the molecule decomposes and either oxidizes
or reduces the metal oxide (catalyst), which in turn changes the oxi-
dation state in the metal oxide from a higher state to a lower state. The
aforementioned conductometric modality works simultaneously with
the thermodynamic modality in that as the explosive molecule inter-
acts with the metal oxide catalyst, electrical resistance of the metal
oxide is monitored and recorded. Resistivity of the metal oxide can
increase or decrease depending on the oxidation/reduction potential
of the decomposition products.
II. EXPERIMENTAL
The orthogonal sensor is constructed on ultrathin alumina ceramic
substrates measuring 1.6 × 0.7 cm. Photolithography and radio fre-
quency (RF) sputtering techniques were used to pattern nickel mi-
croheaters and interdigitated electrodes on these substrates. After the
nickel films were deposited, a 20 μm thick layer of alumina cement
was applied over the microheater to form a passivation layer between
the microheater and metal oxide catalyst. After curing the alumina ce-
ment, the metal oxide catalyst was sputter-deposited onto the cement.
In order to measure the resistance changes across the metal oxide
catalyst after introduction of the analyte, interdigitated “fingers” or
nickel electrodes were patterned onto the catalyst surface. Thus, the
orthogonal sensor was comprised of six leads for attachment to the
connector: four leads for the nickel microheaters and two leads for
electrical resistance measurement. The four leads to each microheater
permitted communication between the microheaters and the digital
control system. A photograph and schematic of the orthogonal sensor
used for trace detection of explosives is shown in Fig. 1.
The metal oxide catalysts investigated in this study include SnO2 ,
Cu2 O, ZnO, FeO, and WO. However, SnO2 , Cu2 O, and ZnO catalysts
will be the primary focus of this article. A digital control system sup-
plies electrical power to the microheaters such that resistance heating
can be controlled using proprietary software. The exact temperature
of the microheater can be determined from the temperature coefficient
of resistance or TCR and resting resistance of the nickel microheater
at room temperature.
A constant current source supplied a small current to the interdigi-
tated fingers such that electrical resistance of the metal oxide could be
measured. The current was varied from 1 to 15 mA, and the nominal
electrical resistance was on the order of 1000 .
VOL. 3, NO. 10, OCTOBER 2019
Fig. 2. Schematic of an apparatus used for explosives testing of an
orthogonal sensor.
Analyte was introduced to the system using a 2-chamber apparatus
(see Fig. 2). Initially, dry air from a pressurized gas cylinder was
delivered to an empty cylinder where the flow was split evenly such that
identical streams were delivered to the catalyst-coated and reference
microheaters. Constant volumetric flow was maintained using mass
flow controllers (Allicat Scientific Mass Flow Controllers with Flow
vision software). At this point, the microheater sensors were heated to
a predetermined set point temperature, and a power/resistance baseline
was established using this carrier gas (air).
At the start of a test, the carrier gas (air) was diverted from the empty
chamber to an analyte chamber containing either solid 2,4-DNT or
TATP. Flow was diverted using mass flow controllers to control the
volumetric flow rate. Explosive vapors were picked up by the dry air
carrier gas and delivered downstream to the active sensor elements. A
schematic of this apparatus is shown in Fig. 2.
When an explosive molecule interacts with the metal oxide cata-
lyst, the heat generated or absorbed by the catalyst in the presence of
the explosive molecule results in a change in electrical power. As a
result of this change in power, the software maintains a constant tem-
perature set point by either adding or subtracting electrical power to
the catalyst-coated microheater. The electrical power change required
to maintain a constant temperature is the thermodynamic heat effect
associated with the analyte-catalyst interaction. This power difference
was monitored and recorded by proprietary software for signal pro-
cessing and compilation of the data. During a typical experimental
run, the microheater was cycled to a temperature of 500 °C and a
15 mA current was supplied from the constant current source to the
interdigitated fingers deposited on the metal oxide. Each experiment
required several minutes to complete since the sensors were allowed
to reach peak response, i.e., the power at which the sensor reaches
equilibrium depends on the response to a specific analyte.
III. RESULTS AND DISCUSSION
Figs. 3 and 4 show two orthogonal sensor responses to TATP and
2,4-DNT in the vapor phase using a SnO2 catalyst. As shown in Figs.
3 and 4, both TATP and 2,4-DNT have an endothermic thermody-
namic response when using a SnO2 catalyst. Here, the SnO2 catalyst
is reduced upon analyte interaction (decomposition products derived
from the TATP and 2,4-DNT explosives), going from a higher ox-
idation state to a lower oxidation state. This reduction reaction is
endothermic in nature, and thus, the power to the sensor is increased
in order to maintain a constant temperature. For our purposes, sensi-
tivity is defined as a ratio of the thermodynamic, or conductometric,
response to the concentration of the target molecule. The thermody-
namic responses shown in Figs. 3 and 4 translate into sensitivities of
0.5 mW/ppm for TATP and 28 mW/ppm for 2,4-DNT, respectively.
The conductometric response corresponds to the change in charge
 VOL. 3, NO. 10, OCTOBER 2019
Fig. 3. Orthogonal sensor responses to 20 ppm TATP utilizing a SnO2
catalyst. Thermodynamic response is highlighted in blue, while conduc-
tometric response is highlighted in orange.
Fig. 4. Orthogonal sensor responses to 180 ppb 2,4-DNT utilizing a
SnO2 catalyst. Thermodynamic response is highlighted in blue, while
conductometric response is highlighted in orange.
carrier concentration in the metal oxide as a result of the correspond-
ing redox reaction. In Figs. 3 and 4, the SnO2 undergoes a reduction
reaction in which the number of oxygen vacancies is increased. The
negative response of the conductometric platform is consistent with
this reduction reaction in that the resistance of the metal oxide de-
creases as it interacts with the explosive molecule due to the increase
in oxygen vacancies. These conductometric responses translate into
sensitivities of 1.5%/ppm for TATP and 94%/ppm for 2,4-DNT.
It has been shown that post-transition metal oxides such as SnO2
and ZnO possess d0 and d10 electron configurations, which can result
in improved sensitivity for conductometric sensor applications [13].
These oxides possess relatively small band gaps (3–4 eV) and, thus,
permit greater exchange of electrons between the catalyst and analyte
[14]. In order to test the effectiveness of these post-transition metal
oxides, orthogonal sensors employing a ZnO catalyst were fabricated.
As shown in Fig. 5, the ZnO orthogonal sensors exhibited endothermic
responses to 2,4-DNT. Here, the ZnO catalyst undergoes a reduction
reaction, going from a higher oxidation state to a lower oxidation
state, which requires more energy to maintain a constant temperature.
This orthogonal sensor exhibited a similar response to 2,4-DNT to
a sensor employing an SnO2 catalyst as shown in Fig. 4. A similar
negative conductometric response also coincided with the change in
charge carrier concentration based on the redox reaction. The ZnO
catalyst displayed sensitivities of 33 mW/ppm for the thermodynamic
platform and 39%/ppm for the conductometric platform.
2000504
Fig. 5. Orthogonal sensor responses to 180 ppb 2,4-DNT utilizing a
ZnO catalyst. Thermodynamic response is highlighted in blue, while
conductometric response is highlighted in red.
Fig. 6. Orthogonal sensor responses to 180 ppb 2,4-DNT utilizing a
Cu2 O catalyst. Thermodynamic response is highlighted in blue, while
conductometric response is highlighted in orange.
A major drawback of current conductometric platforms is an in-
herent limit on selectivity [14]. As shown in the responses above,
sensors employing post-transition metal oxide catalysts display sim-
ilar responses to various explosive analytes. To address this, certain
semiconducting metal oxides, such as CuO, have been used to im-
prove selectivity [14]. Here, the CuO possess a filled valence electron
shell and a small band gap (1.2 eV), allowing for further exchange of
electrons and, thus, better sensitivity. Fig. 6 shows the response of an
orthogonal sensor to 2,4-DNT in the vapor phase using a Cu2 O cata-
lyst. Again, the sensors were heated to 500 °C and a 15 mA current was
supplied to the sensor using a constant current source. Here, the Cu2 O
catalyst was oxidized upon decomposition of the TATP and 2,4-DNT
molecules, resulting in an exothermic response. This response is a
result of the transition from a lower oxidation state to a higher oxida-
tion state, and thus, a decrease in oxygen vacancies and corresponding
decrease in charge carrier concentration. This oxidation reaction, as
opposed to a reduction reaction, makes the Cu2 O catalyst uniquely se-
lective to the 2,4-DNT molecule. Here, the thermodynamic response
displayed a sensitivity of 140 mW/ppm, which represents a significant
increase over previous catalysts. The conductometric response here is
positive (electrical resistance of the Cu2 O increases) upon interaction
with the decomposition products of 2,4-DNT, and an increase in sen-
sitivity of 1250%/ppm was observed. Compared to orthogonal sensors
employing SnO2 or ZnO catalysts, sensors employing Cu2 O catalysts
displayed an extraordinary increase in sensitivity to 2,4-DNT.
2000504
IV. CONCLUSION
Overall, integration of a conductometric platform with the thermo-
dynamic platform lead to unparalleled orthogonality for trace detec-
tion. Here, metal oxide catalysts are utilized to measure the heat effect
associated with selective redox reactions that occur on the catalyst sur-
face. Simultaneously, electrical resistance changes in the oxide that
occur as a result of the catalytic redox reactions are measured. The
experimental results suggest that by combining both sensor platforms,
highly selective responses to TATP and 2,4-DNT resulted in unique
signal-temperature signatures for each explosive so that false positives
could be mitigated. Additionally, by implementing Cu2 O as the cata-
lyst for our orthogonal sensor, improved sensitivity and selectivity to
2,4-DNT was realized.
ACKNOWLEDGMENT
This work was supported by the U.S. Department of Homeland Security, Science and
Technology Directorate, Office of University Programs, under Grant 50503578059. The
views and conclusions contained in this document are those of the authors and should not
be interpreted as necessarily representing the official policies, either expressed or implied,
of the U.S. Department of Homeland Security.
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