Int. J. Appl. Ceram. Technol.

, 2 [5] 401–413 (2005)

Ceramic Product Development and Commercialization

A Brief Overview on Automotive Exhaust Gas Sensors

Based on Electroceramics
Ralf Moos*
Functional Materials, University of Bayreuth, Bayreuth 95447, Germany

Nowadays, ceramic exhaust gas sensors are installed in quantities of millions in automotive exhaust gas systems. Almost any
automobile being powered by a gasoline combustion engine is equipped with at least one zirconia exhaust gas oxygen sensor (l
probe) for detection of the air-to-fuel ratio l. The first part of this short overview focuses on potentiometric as well as on
amperometric zirconia exhaust gas oxygen sensors. It is remarkable that in the past years a leap in manufacturing technology has
occurred from classical ceramic technology to tape and thick-film technology. The advent of novel combustion concepts like lean-
burn operating gasoline direct injection required novel exhaust gas aftertreatment concepts. It pushed the development of the
NOx sensor, which is manufactured in the same technology. It is also shown how development of exhaust gas sensors has always to
be considered in interaction with exhaust gas aftertreatment systems. This elucidates why novel sensors have gained in importance
just recently when stricter emission regulations were announced, meaning that the time is ripe for novel exhaust gas aftertreatment
concepts. Appropriate sensors—ammonia sensors, hydrocarbon sensors, and particulate matter sensors—are still in the R&D
stage. Several possible sensor principles are discussed. The materials that are used for sensors in the automotive exhaust are
electroceramics. Besides ion-conducting zirconia and zirconia cermets, electrically insulating alumina is used for substrate pur-
poses. Novel functional materials in the R&D state are strontium–iron titanate for temperature-independent resistive oxygen
sensing and zeolites for selective detection of specific gases like hydrocarbons or ammonia.

Historical Background mixture to the stoichiometric air-to-fuel mixture.

lo1 denotes operation with air deficiency; l41 stands
In order to meet the emission standards, today al- for operation with air excess. It becomes obvious that a
most all gasoline-propelled cars are equipped with a precise sensor is required to detect l 5 1. In the lean
three-way catalyst (TWC), and are operated under an range, excess oxygen determines the oxygen partial pres-
accurate stoichiometric air–fuel mixture. In Fig. 1 it is sure (pO2) of the exhaust. Around the stoichiometric
shown as to how a TWC converts limited reducing point, pO2 changes by several decades. In the rich range,
(HC, CO) and oxidizing (NOx) exhaust components pO2 is determined by chemical reactions. Figure 2 de-
almost completely around the stoichiometric air-to-fuel picts the l(pO2) behavior schematically.
ratio l 5 1. l is the ratio of the actual air-to-fuel
l Sensors for a Stoichiometric Operation
*Ralf.Moos@uni-bayreuth.de
r 2005 The American Ceramic Society Two sensor concepts exist to determine l 5 1.
402 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

100

80

NOx
conversion / %

60
HC
CO

40

lambda- lambda-
three-way-catalyst
sensor sensor
(TWC)
20
raw emission
emission

0
0.94 0.96 0.98 1.00 1.02 1.04
normalized air-to-fuel ratio

Fig. 1. Conversion of a three-way catalyst versus air-to-fuel ratio l. Inset: arrangement for l 5 1 control and onboard diagnosis.

Resistive Sensors tivated by EA but is pO2 independent,2,3 or by finding

resistive sensor materials that do not depend on tem-
The resistive principle uses the pO2 dependence of perature anymore. The most promising material is
the resistivity of some metal oxides. The resistance of a doped SrTi1
xFexO3
d. It was investigated by different
titania sensor, e.g., Rsensor, shows a monotonous increase groups.4–6 The main disadvantage that impedes its serial
up to about 10
2 bar, approximately following Eq. (1). application at the moment is its instability toward sulfur

 oxides in the exhaust7 that stem from sulfur components
EA
Rsensor / exp ðpO2 Þm ð1Þ in the fuel.
kB T
The exponent m (m  0.2–0.25) determines the sensi- Potentiometric Sensors
tivity. The sensor resistance varies by several decades
around l 5 1. Such sensors are manufactured in hybrid Potentiometric sensors (‘‘Nernst cells’’) dominate
technology using screen-printed thick-film sensor ele- the market. These are solid electrolyte concentration
ments on ceramic alumina tapes that are co-fired. A cells. They measure the oxygen activity toward either an
summary of this kind of sensors is given by Takami.1 outside air reference or in novel embodiments toward an
Although still applied, the market share of these sensors internal pumped reference.
is small. Besides possible stability problems when in- The electroceramic material that is applied for the
stalled very close to the outlet valve where the exhaust solid electrolytes is yttrium partly stabilized zirconia
gas may reach more than 10001C, a disadvantage is the (YSZ). The stabilization has two effects: it impedes
temperature dependency (EA) of the sensor resistance. phase transformations and, hence, increases the mechan-
Therefore, in the past 10 years, different materials and ical strength of the materials. Additionally, it enhances
concepts have been studied either to compensate the the ionic conductivity of the electrolyte. Y31 replaces
temperature dependency of the gas-sensitive sensor ma- Zr41, and to ensure electroneutrality, oxygen vacancies
terial by adding a second sensor element that is also ac- form in the zirconia lattice, enabling oxygen diffusion
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 403

1.2

pO2 changes by several

decades around
= 1

1.0

0.8

0.6

VS / V
0.4

0.2

0.8 0.0
0.8 0.9 1.0 1.1 1.2
increasing temperature

10 –20 10 –16 10 –12 10 –8 10 –4

pO2 / bar

Fig. 2. Normalized air-to-fuel ratio l versus pO2. Note the pronounced pO2 variation around the stoichiometric point (l 5 1). Inset: sensor
voltage VS versus l. After Riegel et al.8

via oxygen vacancies. Below 10001C, the effects of elec- (diagnostic sensor) is installed downstream catalyst (Fig.
tronic conductivity can be neglected. 1, inset). Since the oxygen storage capacity of the cat-
If a YSZ membrane with porous electrodes sepa- alyst is correlated with the conversion efficiency, the
rates two gas chambers (pOA2 and pOB2 ), an electromo- amplitudes of the l oscillations downstream catalyst in-
tive force, VS, can be measured. crease with ongoing catalyst deterioration. The ampli-
! tude ratio of both l probes is a measure for the catalyst
kB T pOA
2 efficiency.8 Utilizing the signal of the second sensor, an
VS ¼ ln ð2Þ
4e pOB2 advanced trim control allows to adjust l 5 1 even more
exactly.
If the sensor operation temperature is 7351C and air is Conventional and well-known l probes are made
used as a reference (pOB2  0.2 bar), a voltage difference of a thimble-type zirconia ceramic element. Because this
of 50 mV per decade pO2 difference occurs. According contribution focuses on novel concepts, the reader is
to Fig. 2 (inset), the sensor voltage varies by a few hun- referred to Wiedenmann et al.,9 where a detailed de-
dred mV around l 5 1, leading to a very steep, l scription of the conventional thimble-type l probe and
switch-like characteristic. its development is outlined.
Such l probes are installed upstream of TWC. In a Newer developments use planar zirconia multilayer
simplified consideration, they can be seen as a binary technology. They are characterized by reduced warmup
sensing element in the l control circuit. In operation, time, smaller size, lower weight, and, most importantly
after the cold start phase has finished, l oscillates by cost-effective production. Figure 3 schematically de-
around l 5 1 with a frequency in the order of 1 Hz, picts a planar l probe (Fig. 3a, exploded view; Fig. 3b,
depending on engine operation conditions.8,9 As the sectional view of the sensor tip). The manufacturing
catalyst stores oxygen, the l oscillations are buffered, process resembles microelectronic hybrid production.
leading to catalyst efficiencies of almost 100%. Ceramic YSZ tapes are cast and cut to the right size.
In order to in situ monitor the conversion efficiency Vias ( 5 contact holes) are punched. Heater, electrodes,
of TWCs (onboard diagnosis, OBD), a second l probe conductor tracks, contact pads, porous protection layers,
404 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

porous protection layer

exhaust electrode

sensor sheet

reference electrode

air duct sheet

alumina insulation

platinum Heater

alumina insulation

heater sheet

contact pads

Fig. 3. (a, left) Exploded view of a commercial planar l probe (Robert Bosch GmbH, Germany; after Robert Bosch GmbH51). (b, right)
Sectional view of the sensor tip as indicated by the dashed line.

and insulation layers are screen printed on these tapes. A concept that further reduces size, light-off time,
The entire sensor element consists of a heater sheet, air production costs, and that excludes errors due to an in-
duct sheet, and sensor sheet. The heater sheet is covered stable air reference uses a pumped reference (Fig. 4, after
with an alumina insulation film, serving as a base for the Makino et al.10). Due to a voltage V0, a small current IcP
platinum heater meander, which is also insulated by an (in the order of some mA) flows through the cell. The
alumina layer. Porous platinum electrodes are printed current IcP is determined by the series resistance RP.
on both sides of the sensor sheet. A porous layer protects Oxygen ions are forced through the cell and form
the exhaust electrode. In operation, the punched air an oxygen pseudoreference inside the sensor (pOB2 ).
duct sheet serves as an air reference. The tapes are The internal reference can also be implemented as a
stacked, laminated, individualized, and co-fired. The small porous chamber. This concept has been serialized
resulting monolithic ceramic sensor element can be recently.
heated to operation temperature within less than 10 s
consuming only 7 W heating power.8 For even faster
sensors, an optimized heater design leads to a further Wide Band l Sensors
reduced light-off time.10
It is also possible to utilize alumina as a material for The planar manufacturing technology also serves as
heater sheet and air duct sheet. Its advantages are its a basis for a combined potentiometric/amperometric
good thermal conductivity, its very high resistivity, and sensor that can determine l in a wide range between
its cost-effeciveness compared with YSZ. Problems orig- approx. 0.7 and 10. The sensor consists of four zirconia
inate from joining alumina and YSZ in the green state sheets (Fig. 5). The heater sheet and the air duct sheet
and can be addressed to delamination caused by differ- are mainly identical to the planar l probe (Fig. 3b).
ent sinter shrinkage behavior and by differences in the Here, the sensor sheet forms a Nernst concentration cell
coefficient of thermal expansion.11 that determines pO2 behind a diffusion barrier toward
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 405

IcP

V0
O 2–

RP

Fig. 4. Sketch of a potentiometric l sensor with pumped reference (after Makino et al.10).

the reference channel (air duct). The diffusion barrier oxygen reference. As a result, one YSZ layer can be
between the sensor sheet and the membrane sheet is saved, leading to further reduced size and light-off time
made of a porous oxide ceramic. The voltage of the and also to decreased thermo-mechanical stress.13,14
reference electrode is controlled electronically to
Vref  450 mV. According to Fig. 2 (inset), this is
equivalent to l 5 1. Hence, pO2 at the inner pumping NOx Sensors
electrode is always adjusted to l 5 1. If the exhaust is
lean, oxygen diffuses from the exhaust through the dif- Novel gasoline direct injection engines need a dif-
fusion barrier to the inner pumping electrode. IP is the ferent nitrogen oxide abatement concept using NOx
electronic current that is necessary to mainatin l 5 1 at storage catalysts (NSC). During a lean phase of about
the inner pumping electrode. Since IP is diffusion lim- 2 min, the catalyst adsorbs NOx. Right before the stor-
ited, it is almost proportional to the exhaust oxygen age capacity is exhausted and the catalyst begins to allow
concentration.12 If the exhaust is rich, water is electro- NOx to pass, the engine is operated richly for a few
chemically decomposed at the exhaust electrode and the seconds. During this ‘‘regeneration phase,’’ stored NOx
oxygen ions formed are pumped into the sensor, i.e., IP is released and reacts with the reducing components that
is negative. The IP(l) plot (Fig. 6) clearly shows the are in the rich exhaust. After regeneration, the engine is
wide band characteristic of such a sensor. operated leanly again. This complex process works best
Very recent developments are combined ampero- with an exhaust gas sensor that is mounted downstream
metric–potentiometric sensors that do not need an air NSC, providing threefold functionality: First, an NOx
reference. A pumped reference chamber serves as an output to determine increasing nitrogen oxides emis-

diffusion hole exhaust gas; pO2 , cO2

porous protection layer

diffusion barrier
IP
Vref
membrane sheet O 2–
+
sensor sheet
–

air duct sheet

heater sheet

Fig. 5. Sensor tip of a commercial amperometric/potentiometric wide-band l sensor (type LSU, Robert Bosch GmbH, Germany; after Robert
Bosch GmbH51).
406 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

3 Based on the zirconia planar technology, a multi-

functional NOx sensor was developed,15 as shown in
Fig. 7. Oxygen or NOx diffuse from the exhaust
2 through a first diffusion barrier (A) to a first chamber
pumping current IP /mA

(B). Oxygen is pumped out of (B). The pumping cur-

rent IP1 is almost proportional to the pO2 of the ex-
1 haust. Due to the pumping voltage VP1, an almost
oxygen-free but not reducing atmosphere is established
in (B). pO2 in (B) is closed-loop controlled by the elec-
0
tromotive force between (3) and (4), i.e., between cham-
ber (B) and air. The electrodes of the first pumping cell
are of catalytically inactive gold–platinum alloys. There-
–1
fore, NOx is not decomposed there and diffuses through
a second diffusion barrier (C) into a second chamber
(D). NOx is electrochemically decomposed at the cath-
–2
0.7 1.0 1.3 1.6 1.9 2.2 2.5 ode (5) of the second pumping cell due to the pumping

voltage VP2.The resulting oxygen ions are pumped
through the second pumping cell to the air duct. There,
Fig. 6. Electronic pumping current IP of the sensor in Fig. 5 (after they are re-oxidized. Since there is almost no free oxygen
Robert Bosch GmbH51). in (D), the resulting pumping current IP2 results only
from decomposed NOx and, therefore, depends almost
linearly on the NOx concentration of the exhaust. Since
sions, indicating that NOx-storage capacity is exhausted. most of the reducing components are oxidized in (B),
In addition to this, the precise end of the regeneration the sensor shows a low cross-sensitivity toward CO or
phase, which is indicated by a l decrease from stoic- HC.15 However, it is sensitive to ammonia.16 The volt-
hiometric to rich, has to be detected in order to prevent age VS between exhaust electrode (1) and air reference
HC or CO breakthroughs. For general control purpos- electrode (6) follows Eq. (2). VS(l) shows the charac-
es, a wide-band l sensor is desirable. teristic of a potentiometric l probe and can be used to

1 2 3 4 5 6
A B C D

IP2 VP1 first pumping cell sheet

VS spacer sheet
second pumping cell sheet
air duct sheet
VP2 IP1
heater sheet

heater sheet

Fig. 7. Multifunctional zirconia NOx sensor. The sensor has three different functionalities: IP1 is a measure for pO2, IP2 is proportional to the
NOx concentration. VS is a l 5 1-sensor.
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 407

determine the end of the regeneration phase in gasoline sensors is their cross sensitivity to oxygen, water, and/or
direct injection engines (GDI).17 NOx.
One main problem of these sensors are the small At the moment, several types of sensors are under
electronic currents that occur. A rough estimation leads development for automotive exhaust gas application.
to a sensitivity in the range of some nA/ppm NOx. Due They are considered to meet the requirements with re-
to this low signal level, leak currents in the ceramic spect to long-term stability and target cost. The most
could have an influence on the sensor signal. As can be straightforward approach uses the cross sensitivity to-
seen from Fig. 7, the setup is very complex and the ward ammonia of zirconia NOx sensors for SCR system
contrast between functionality and low system costs be- control.26
comes obvious. Research efforts were undertaken to In metal insulator SiC field effect transistors, the
avoid the complex setup with its many production steps gates are covered with a catalytically active metal like
by using a sensor design in a conventional thick-film porous platinum.27 With increasing ammonia concen-
screen printing technique.18–20 However, up to now, no tration, the drain current increases (at constant drain
sensor of this type has been commercially available. A voltage). The voltage shift of the I(V ) curve (where
very comprehensive overview (unfortunately as of 1999) I 5 const.) is the sensor signal.28 Sensors have been suc-
on ceramic NOx sensors is given in Ménil et al.21 cessfully tested in real exhaust gas. However, as men-
tioned in Wingbrant et al.,27 varying speed and load
Ammonia Sensors make the interpretation of the signals difficult. One
technological challenge is the integration of SiC with
Due to more stringent emission standards for ceramic heaters.
heavyduty vehicles in conjunction with increased pres- Recently, a resistive-type ammonia sensor was dis-
sure for fuel efficiency, the European automotive indus- closed. A ‘‘super strong acidic’’ material was suggested as
try has decided to adopt the ammonia selective catalytic an ammonia-sensitive material.29 Promising results with
reduction (SCR) exhaust gas aftertreatment process for respect to sensitivity and long-term stability (6001C,
automotive applications. In the U.S., this system is also 100 h, air) was reported for mixtures of WO3 and YSZ.
under consideration. Ammonia SCR technology was Mixed potential sensors were also investigated for
originally developed for coal power plants and allows to ammonia sensing. The sensor setup resembles the one
reduce NOx in lean atmospheres. Ammonia-forming shown in Fig. 3. Now, the exhaust electrode consists of
substances like urea–water solutions are added to the vanadia-based materials, which seem to form very se-
exhaust and serve as reducing agents. Unfortunately, lective electrodes. In Wang et al.30 a huge variety of
NOx conversion depends upon temperature, pO2, NO2 materials were tested. From Wang et al.30 it can be cal-
concentration, space velocity, and also on the amount of culated, however, that the sensor temperature is signif-
previously stored ammonia. Vehicles are operated under icantly lower than required for l sensing.
continuously changing speed and load conditions. To
minimize the injected amount of urea and to avoid am- Zeolite Ammonia Sensor
monia slip, a closed-loop controlled system using an
ammonia exhaust gas sensor is desirable. Ammonia sen- Another promising approach is based on a zeolite
sors offer a convenient method for OBD of the ammo- thick film as a functional layer. As depicted in the sim-
nia dosing system. plified setup of a sensor element (Fig. 8), electrically
insulating alumina serves as a substrate. A passivated
Sensor Principles thick-film platinum structure on the bottom is used for
heating and temperature control. Interdigital electrodes
Many approaches for the detection of ammonia are on the top side form a thick-film capacitor. It is covered
proposed in the literature; examples are doped semi- by a zeolite film that selectively changes its complex
conducting metal oxides like tungsten oxide,22 molyb- impedance with the ammonia concentration. During
denum oxide,23 or indium oxide.24 Sensors based on the sensor development, the zeolite material was selected
Cr2Ti2
xO7
2x are already commercially available for with respect to selectivity and long-term stability. The
ammonia detection in air for non-automotive applica- main parameters of the variation were the type of
tions.25 The main disadvantage of resistive metal oxide zeolite, its Na/H ratio, and its module. Impedance
408 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

exhaust gas; cNH3

zeolite film

interdigital
capacitor

alumina substrate

platinum heater

ceramic cover film

Fig. 8. Simplified cross-section of the zeolite NH3 sensor. After Moos et al.31

spectroscopy data of many different zeolites were taken ance (derived from the RC-equivalent circuit, sensor
between 2001C and 5001C in the 20 Hz to 1 MHz temperature 4201C) taken at 1 MHz follows the am-
range. When plotted in the complex resistance plane, monia content, reaches constant final values, and recov-
semicircles appear for almost all investigated samples at ers fast. The most important parameter for selectivity is
all temperatures.31 Therefore, the resulting spectra can the module. All H-ZSM5 zeolites are sensitive to am-
be interpreted by an resistance capacity (RC) parallel monia, but only low alumina zeolites ( 5 high module)
equivalent circuit. For an ammonia-sensitive zeolite show low cross sensitivities. The ammonia sensor does
film, at a fixed suitable working frequency, both R not have cross-sensitivity with respect to the presence of
and C depend on the ammonia concentration of the hydrocarbons, carbon monoxide, and oxides of nitro-
exhaust. Figure 9 shows a typical lab test run for an H- gen, i.e., it is not affected by these gases. In engine test
ZSM5 zeolite with a module of 140. The baseline gas benches the sensor showed very promising results.31
contained 10 vol% O2 and 5 vol% H2O. After stepwise The above-described behavior can be explained
changing the ammonia concentration, the sensor resist- qualitatively by considering the ammonia-supported

50

45 0 ppm 0 ppm

5 ppm
sensor resistance R / k


10 ppm
40
20 ppm

35 40 ppm

60 ppm
30 80 ppm

100 ppm
25

20
0 3 6 9 12 15 18 21 24 27 30
t / min

Fig. 9. Example of a zeolite NH3 sensor. Data: material H-ZSM5 sensor (module 140), R (at 1 MHz, 4201C). Background gas: 10 vol%
O2, 5 vol% H2O, N2 balance. After Moos et al.31
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 409

transport of protons above a certain temperature, where Hydrocarbon Sensors

they can be regarded as solvate free.32 More information
on the steps that helped to find an appropriate zeolite Possible Application and Requirements
can be obtained from Moos et al.31 and Plog et al.33
It should be noted that at the moment no serial Applied downstream TWC hydrocarbon sensors
vehicle is equipped with an ammonia sensor; however, it can measure the limited components directly, enabling
was announced that an ammonia sensor will be serial- a direct OBD without determining oxygen storage ca-
ized soon.34 pacity indirectly as a measure for catalyst efficiency. For
this application the sensor has to meet highest require-
ments. Gas temperatures can reach almost 10001C and
Particulate Matter Sensors the oxygen content is almost zero. In addition to that,
the sensor has to deal with HC concentrations of only a
Possible Application and System Requirements few ppms. Milder conditions occur for the OBD of
close-coupled oxidation catalysts of diesel engines. The
Particles of diesel-propelled vehicles, especially re-
maximum temperature remains below 6001C and there
spirable particles in the sub-micron range, may affect
is always excess oxygen present in the exhaust. In gaso-
human health. Diesel particulate emissions are a com-
line direct injection engines, hydrocarbon sensors can
plex mixture of solid and liquid components. The main
detect the end of the regeneration phase more precisely
constituents are soot, various adhered hydrocarbons,
than a l sensor. In particular, hydrocarbon sensors can
and ashes. Ceramic diesel particulate filters (DPF) are
be applied for OBD in these systems. Furthermore, they
effective means for reducing particulate matter emis-
can be used for OBD of close-coupled oxidation cata-
sions from diesel vehicles. During operation, the filter
lysts for GDI engines.
pores become clogged and the exhaust gas backpressure
increases. Then, filter regeneration has to be initiated by
raising the exhaust temperature up to the soot ignition Sensor Principles
temperature. All regeneration strategies have in com-
mon that they consume additional fuel. Most hydrocarbon sensors under development use
Exhaust gas soot sensors can help to find the opti- the mixed potential principle. Here, the electromotive
mal period between two regeneration events and they force between two different electrodes located on a solid
can be used for OBD purposes. However, a correlation electrolyte is the sensor raw signal. Usually, YSZ is used
between the sensor output signal and gravimetrically as a solid electrolyte, but fast sodium ion conductors like
determined particulate mass has to be found. b00 -alumina or proton conductors are disclosed as well.
One electrode is made of a catalytically active conduc-
Short Overview on Sensor Principles tor, like platinum. A catalytically inactive material like
gold serves as a counter electrode. Since these sensors are
In the scientific literature, only a few soot sensors operated in non-equilibrium, they are operated best
have been published. This is in strong contrast to patent around some hundred 1C. Beyond this, their sensitivi-
specification, where several principles to detect soot in ty decreases. Below, their response becomes slow and
the automotive exhaust are reported. the internal resistance becomes too high. It is a general
Frequent approaches use the conductometric prin- disadvantage of this type of sensor that the output signal
ciple. Two metallic electrodes are located on porous in- around l 5 1 depends strongly on the oxygen partial
sulating ceramic substrates. Conductive soot particles pressure of the exhaust. Besides finding an optimum
covering the space between the electrodes lead to a re- operation temperature, the main parameters of the sen-
sistance decrease. A good relationship between pressure sor development are the electrode materials. Informa-
difference and sensor resistance has been reported.35 An tion on electrode materials and on the theory of mixed
integrated heater burns adhered soot and regenerates the potential sensors can be obtained from Miura et al.,37
sensor surface. The time interval between two regener- Zosel et al.,38 Guillet et al.,39 and Zosel et al.40 A com-
ation events can also be a measure for exhaust soot con- mercialized sensor with a proven long-term stability in
centration. Initial results show that such sensors might real exhaust especially designed for lean-burn diesel engine
be suitable for OBD purposes36 as well. exhausts is reported in Riegel et al.8 and Moser et al.41
410 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

Since these mixed potential sensors work well only that the sensor signal increases with increasing chain
in lean atmospheres, it was disclosed to combine them length of the hydrocarbons.
with an oxygen pumping cell.42 From a technological The integrated sensor was installed downstream the
point of view, integration of a high-temperature pump- catalyst in the exhaust pipe of an internal combustion
ing cell and a ‘‘low’’-temperature sensor in one device is engine. The output signal was recorded and plotted
difficult. Additionally, in exhausts of gasoline engines against the hydrocarbon concentration, which was ob-
usually higher temperatures occur. This leads to long- tained from a conventional flame ionization detector
term stability problems of the sensor signal. Further- (FID). Secondary air (a) was injected behind the catalyst
more, one has to ensure that hydrocarbons do not be- but in front of the sensor (b) to ensure a lean sensor
come oxidized on the hot catalytically active electrodes operation. Two catalysts were compared: a fresh one
of the pumping cell. and an aged one. Depending on the catalyst status as
Another concept uses two resistive oxygen sensors well as on the speed-load conditions, distinct hydrocar-
of the same material; a catalytically coated and a non- bon concentrations were measured. The comparison of
coated one.43 The resistance difference (or the resistance output signal and hydrocarbon concentration reflects a
ratio) is a measure for the difference between equilibri- good correlation, possibly allowing to detect the catalyst
um and non-equilibrium. A porous thick-film titanate conversion status.44
sensor is compared with a sensor that was activated by
impregnation with a hexachloroplatinate solution. The Zeolites for Hydrocarbon Sensing
difference in the lean range is a measure for the net
concentration of combustibles in the exhaust. A dem- A very selective zeolite-based hydrocarbon sensor
onstration of the capabilities of this system is given in has a setup similar to the ammonia sensor described in
Fleischer et al.44 Activated and non-activated sensors are Fig. 8.46 A platinum-doped Na–Y–zeolite thick
integrated on one alumina substrate. The ratio of both film (PtNaY) is deposited on a transducer with an
sensor resistances was calculated, transformed in an interdigital electrode structure. As can be seen from
analogous output signal. In Sahner et al.,45 it was shown Fig. 10, a strong increase of the normalized resistance

400

T = 350 °C

300
resistance change ∆R /R / %

200
1000 ppm C4 H10

100

1000 ppm CO
0
1000 ppm H2

0.1 1 10
f/ kHz

Fig. 10. Normalized resistance of a zeolite hydrocarbon sensor toward some reducing exhaust components (after Plog et al.46).
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 411

below 100 Hz (assuming RC parallel equivalent circuit) a zeolite cover on top. Resistive SrTi1
xFexO3
d sensors
occurs when the sensor is exposed to butane. There is (STF) are known to be sensitive to hydrocarbons.
almost no cross-sensitivity towards CO and H2. Water If such sensors are covered with platinum-exchanged
vapor affects the sensor signal only very slightly above Na-ZSM5 zeolites they become very selective. Figure 11
2001C. Unfortunately, published data end at 4001C. It compares the response of an uncovered STF thick-film
is remarkable that such sensors show a good sensitivity sensor (x 5 0.2) with the same sample but subsequently
even in rich atmospheres.47 A reason for this might be covered with a zeolite film,48 both at 4251C in
that the butane-sensing effect of resistive zeolite sensors air. Different exhaust components were added succes-
is related to its catalytic properties: PtNaY zeolites have sively. Apparently, the zeolite-covered sensor is not sen-
a high catalytic activity for the conversion of hydrocar- sitive to H2, NO, CO, and C3H6, whereas the
bons to H2O and CO, and hence they show a strong sensitivity to C3H8 is even slightly increased. Addition-
response toward butane, whereas the undoped and lowly ally, it was observed that at this temperature STF sensors
catalytically active NaY form is almost insensitive. are only slightly sensitive to oxygen variations in the
A preliminary model46 considers that the mobile exhaust.49 Very similar results were observed with
sodium ions are hindered by the complex catalytic re- dispersed PtNaY zeolites in n-type semiconducting
action of butane, as all three steps of catalytic conversion TiO2 (anatase form).50 Since TiO2 (like almost all
(adsorption, reaction, desorption) on platinum clusters n-type semiconducting sensor materials) is cross-sensi-
within the zeolite pores take some time for the large tive to water, it is suggested that the response to propane
butane molecule at 3501C. Platinum is covered with a is due to water that forms when hydrocarbons become
number of molecules per time unit that reduce the mo- oxidized.
bility of the sodium ions. For H2 and CO, however, the
catalytic reaction is very fast, especially at 3501C. It is
assumed that both components are completely oxidized Status of the Hydrocarbon Exhaust Gas Sensor
by PtNaY. Therefore, the coverage of platinum with
molecules is small per time unit and almost no hin- The demand from automotive engineers for hydro-
drance of sodium ions occurs. Since the suggested main carbon sensors has existed for more than 10 years,
effect is decreased sodium ionic mobility, oxygen should especially for OBD purposes. However, up to now,
not cause pronounced signal changes. the legal requirements have been met with the above-
An excellent alternative with respect to selectivity mentioned dual l sensor concept and, therefore, no hy-
might be a combination of p-type semiconductors with drocarbon sensor has been serialized.

air + air + air + air + air +

500 ppm C3H8 500 ppm C3H6 1000 ppm H2 500 ppm NO 500 ppm CO
700

600
T = 425 °C
500
R/k 

400
uncovered
300 zeolite covered

200
air air air air air
100
0 20 40 60 80 100 120
t/ min

Fig. 11. Sensor response of an uncovered and a Pt-NaZSM5-covered thick-film STF sensor (x 5 0.2) that is successively exposed to several
components of automotive exhaust (after Sahner et al.48).
412 International Journal of Applied Ceramic Technology—Moos Vol. 2, No. 5, 2005

24. V. Romanovskaya, M. Ivanovskaya, and P. Bogdanov, ‘‘A Study of Sensing

References Properties of Pt- and Au-Loaded In2O3 Ceramics,’’ Sensors Actuat. B, 56
31–36 (1999).
1. A. Takami, ‘‘Development of Titania Heated Exhaust Gas Oxygen Sensor,’’ 25. B. C. Tofield, P. T. Moseley, J. O. W. Norris, and D. E. Williams, U.K.
Ceram. Bull., 67 1956–1960 (1988). Patent Specification, GB 2202948, 1987.
2. J. Gerblinger, H. Meixner, and P. Kleinschmidt, World Patent Specification 26. R. Hammerle, ‘‘Urea SCR and DPF System for Diesel Sport Utility Vehicle
WO 1990/3569 (1990). Meeting Tier II Bin 5,’’ 9th Diesel Engine Emissions Reduction (DEER) Work-
3. N. Izu, W. Shin, I. Matsubara, N. Murayama, N. Oh-hori, and M. Itou, shop, Newport, RI, 2003.
‘‘Temperature Independent Resistive Oxygen Sensors Using Solid Electrolyte 27. H. Wingbrant, H. Svenningstorp, P. Salomonsson, D. Kubinski, J. H. Visser,
Zirconia as a New Temperature Compensating Material,’’ Sensors Actuat. B, and A. Lloyd Spetz, ‘‘Using a MISiCFET Sensor for Detecting NH3 in SCR
108 216–222 (2005). Systems,’’ Proceedings IEEE Sensors 2003, Toronto, Canada, 428–433,
4. R. Moos, W. Menesklou, H. J. Schreiner, and K. H. Härdtl, ‘‘Materials for 2003.
Temperature Independent resistive Oxygen Sensors for Combustion Exhaust 28. A. Lloyd Spetz, L. Unéus, H. Svenningstorp, P. Tobias, L. -G. Ekedahl, O.
Gas Control,’’ Sensors Actuat. B, 67 178–183 (2000). Larsson, A. Göras, S. Savage, C. Harris, P. Mårtensson, R. Wigren, P. Sal-
5. R. Moos, F. Rettig, A. Hürland, and C. Plog, ‘‘Temperature-Independent omonsson, B. Häggendahl, P. Ljung, M. Mattsson, and I. Lundström, ‘‘SiC
Resistive Oxygen Exhaust Gas Sensor for Lean-Burn Engines in Thick-Film Based Field Effect Gas Sensors for Industrial Applications,’’ Phys. Stat. Sol.
Technology,’’ Sensors Actuat. B, 93 42–49 (2003). (A), 185 15–25 (2001).
6. A. Rothschild, S. J. Litzelman, H. L. Tuller, W. Menesklou, T. Schneider, 29. H. Nishiyama, S. Kakimoto, R. Inoue, H. Yokoi, N. Ishida, T. Oshima, S.
and E. Ivers-Tiffée, ‘‘Temperature-Independent Resistive Oxygen Sensors Sugaya, K. Imaeda, T. Hattori, and A. Satsuma, European Patent Specification,
Based on SrTi1
xFexO3
d Solid Solutions,’’ Sensors Actuat. B, 108 231–237 EP 1403637, 2002.
(2005). 30. D. Y. Wang, W. T. Symons, R. J. Farhat, C. A. Valdes, E. M. Briggs, K. K.
7. F. Rettig, R. Moos, and C. Plog, ‘‘Poisoning of Temperature Independent Polikarpus, and J. Kupe, United States Patent Application, US 2004/0118703,
Resistive Oxygen Sensors by Sulfur Dioxide,’’ J. Electroceram., 13 733–738 2004.
(2004). 31. R. Moos, R. Müller, C. Plog, A. Knezevic, H. Leye, E. Irion, T. Braun,
8. J. Riegel, H. Neumann, and H. -M. Wiedenmann, ‘‘Exhaust Gas Sensors for K. -J. Marquardt, and K. Binder, ‘‘Selective Ammonia Exhaust Gas
Automotive Emission Control,’’ Solid State Ionics, 152–153 783–800 (2002). Sensor for Automotive Applications,’’ Sensors Actuat. B, 83 181–189
9. H. -M. Wiedenmann, G. Hötzel, H. Neumann, J. Riegel, F. Stanglmeier, and (2002).
H. Weyl, ‘‘Exhaust Gas Sensors,’’ Automotive Electronics Handbook, 2nd 32. M. E. Franke, U. Simon, R. Moos, A. Knezevic, R. Müller, and C. Plog,
edition, ed. R. K. Jurgen. McGraw-Hill, New York, 1999 6.1–6.25. ‘‘Development and Working Principle of an Ammonia Gas Sensor based on
10. K. Makino, H. Nishio, T. Okawa, K. Yabuta, and K. Shimamura, ‘‘Compact a Refined Model for Solvate Supported Proton Transport in Zeolites,’’ Phys.
Thick Film Type Oxygen Sensor,’’ SAE Paper 1999-01-0933, 1999. Chem. Chem. Phys., 5 5195–5198 (2003).
11. S. Naito, T. Sugiyama, and Y. Nakamura, ‘‘Development of Planar Oxygen 33. C. Plog, W. Maunz, and R. Müller, United States Patent Specification, US
Sensor,’’ SAE Paper 2001-01-0228, 2001. 6,069,013, 1997.
12. H. Dietz, ‘‘Gas-Diffusion-Controlled Solid-Electrolyte Oxygen Sensors,’’ 34. DaimlerChrysler (ed.), ‘‘Thinking Ahead,’’ DaimlerChrysler Hightech Report,
Solid State Ionics, 6 175–183 (1982). 1/2004, 46–48, 2004.
13. L. Diehl, T. Wahl, and J. Riegel, ‘‘Ceramic Aspects of Automotive Exhaust 35. J. P. Demethon and B. Martin. United States Patent Specification, US
Gas Sensors,’’ Materials Week Munich, Germany, 2003. 6,107,603, 1997.
14. U. Alkemade and B. Schumann, ‘‘Engines And Exhaust After Treatment 36. M. Bouchez and J. B. Dementhon, ‘‘Strategies for the Control of Particulate
Systems For Future Automotive Applications,’’ Solid State Ionics 15, July Trap Regeneration,’’ SAE Paper, 2000-01-0472, 2000.
17–22, 2005, Baden-Baden, Germany. 37. N. Miura, T. Raisen, G. Lu, and N. Yamazoe, ‘‘Highly Selective CO Sensor
15. N. Kato, K. Nakagaki, and N. Ina, ‘‘Thick Film ZrO2 NOx Sensor,’’ SAE Using Stabilized Zirconia and a Couple of Oxide Electrodes,’’ Sensors Actuat.
Conference Paper 960334, 1996. B, 47 84–91 (1998).
16. N. Kobayshi, A. Yamashita, O. Naito, T. Setoguchi, and T. Murase, ‘‘De- 38. J. Zosel, D. Westphal, S. Jakobs, R. Müller, and U. Guth, ‘‘Au–Oxide Com-
velopment of Simultaneous NOx/NH3 Sensor in Exhaust Gas,’’ Mitsubishi posites as HC-Sensitive Electrode Material for Mixed Potential Gas Sensors,’’
Technol. Rev., 38 126–130 (2001). Solid State Ionics, 152–153 525–529 (2002).
17. H. Zhang, C. Pfleger, and B. Lemire, ‘‘Integration eines Smart NOx-Sensors 39. N. Guillet, R. Lalauze, and C. Pijolat, ‘‘Oxygen and Carbon Monoxide Role
im Abgasstrang für die Benzindirekteinspritzung (Integration of a Smart on the Electrical Response of a Non-Nernstian Potentiometric Gas Sensor;
Exhaust gas NOx Sensor for Gasoline Direct Injection),’’ 21st International Proposition of a Model,’’ Sensors Actuat. B, 98 130–139 (2004).
Engine Symposium, Vienna, 2000. 40. J. Zosel, R. Müller, V. Vashook, and U. Guth, ‘‘Response Behavior of Per-
18. P. Schmidt-Zhang, K. P. Sandow, F. Adolf, W. Göpel, and U. Guth, ‘‘Novel ovskites and Au/Oxide Composites as HC-Electrodes in Different Combus-
Thick Film Sensor for Simultaneous O2 and NO Monitoring in Exhaust tibles,’’ Solid State Ionics, 175 531–533 (2004).
Gases,’’ Sensors Actuat. B, 70 25–29 (2000). 41. T. Moser, F. Stanglmeier, B. Schumann, and S. Thiemann-Handler, ‘‘Sensor
19. E. Magori, G. Reinhardt, M. Fleischer, R. Mayer, and H. Meixner, ‘‘Thick in planarer Dickschichttechnik zur Messung von Kohlenwasserstoffen im
Film Device for the Detection of NO and Oxygen in Exhaust Gases,’’ Sensors Abgas von Kraftfahrzeugen (Planar Thick-Film Sensor for Measuring
Actuat. B, 95 162–169 (2003). Hydrocarbons in Automotive Exhausts),’’ Proceedings of ‘‘Sensoren und
20. A. Palmqvist, E. Jobson, L. Andersson, R. Granbro, M. Wendin, L. Megas, P. MeX systeme’’, Ludwigsburg, Germany, March 13–14, 2000, in VDI-Berichte
Nisius, A. Wiartalla, G. Lepperhoff, P. Blakeman, T. Ilkenhans, D. Webster, 1530, VDI-Verlag, Düsseldorf, 159–167, 2000.
G. Haeffler, P. Van de Voorde, P. Schmidt-Zhang, U. Guth, and M. Wallin, 42. E. Logothetis and R. Soltis, United States Patent Specification, US 5,250,169,
‘‘LOTUS: A Co-Operation for Low Temperature Urea-Based Selective Cat- 1991.
alytic Reduction of NOx,’’ SAE-Paper, 2004-01-1294, 2004. 43. A. Bausewein, E. Chemisky, H. Meixner, B. Lemire, and W. Schürz, World
21. F. Ménil, V. Coillard, and C. Lucat, ‘‘Critical Review of Nitrogen Monoxide Patent Specification, WO 99/56118, 1999.
Sensors for Exhaust Gases of Lean Burn Engines,’’ Sensors Actuat. B, 67 1–23 44. M. Fleischer, A. Bausewein, S. Kornely, and H. Meixner, ‘‘Unselektive und
(2000). selektive Abgassensoren auf der Basis hochtemperaturstabiler Metal-
22. C. N. Xu, N. Miura, Y. Ishida, K. Matsuda, and N. Yamazoe, ‘‘Selective loxidhalbleiter (Unselective and Selective Exhaust Gas Sensors Based on
Detection of NH3 Over NO in Combustion Exhausts by Using Au and High-Temperature Stable Metal Oxide Semiconductors),’’ Proceedings of
MoO3 Doubly Promoted WO3 Element,’’ Sensors Actuat. B, 65 163–165 ‘‘Sensoren und MeX systeme’’, Ludwigsburg, Germany, March 13–14, 2000,
(2000). in VDI-Berichte 1530, VDI-Verlag Düsseldorf, 135–144, 2000.
23. A. K. Prasad, P. I. Gouma, D. J. Kubinski, J. H. Visser, R. E. Soltis, and 45. K. Sahner, M. Fleischer, E. Magori, H. Meixner, J. Deerberg, and R. Moos,
P. J. Schmitz, ‘‘Reactively Sputtered MoO3 Films for Ammonia Sensing,’’ ‘‘HC-Sensor for Exhaust Gases Based on Semiconducting Doped SrTiO3 for
Thin Solid Films, 436 46–51 (2003). On-Board Diagnosis,’’ Sensors Actuat. B (2005) in press.
www.ceramics.org/ACT Brief Overview on Automotive Exhaust Gas Sensors 413

46. C. Plog, W. Maunz, P. Kurzweil, E. Obermeier, and C. Scheibe, ‘‘Combus- 49. K. Sahner, R. Moos, M. Matam, and M. Post, ‘‘Thick and Thin Film P-Type
tion Gas Sensitivity of Zeolite Layers on Thin-Film Capacitors,’’ Sensors and Conducting Hydrocarbon Sensors—a Comparative Study,’’ Proceedings of the
Actuat. B, 24–25 403–406 (1995). IEEE Sensors 2003, Toronto, Canada, 926–931, 2003.
47. C. Plog and W. Maunz, United States Patent Specification, US 5,965,451 50. J. Trimboli and P. K. Dutta, ‘‘Oxidation Chemistry and Electrical Activity of
(1996). Pt on Titania: Development of a Novel Zeolite-Filter Hydrocarbon Sensor,’’
48. K. Sahner, R. Moos, M. Matam, J. Tunney, and M. Post, ‘‘Hydrocarbon Sensors Actuat. B, 102 132–141 (2004).
Sensing with Thick and Thin Film P-Type Conducting Perovskite Materi- 51. Robert Bosch GmbH, Company Information, e.g., http://www.boschusa.com/
als,’’ Sensors and Actuat. B, 108 102–112 (2005). AutoOrigEquip/Sensors/DevExhSensors/.