CHAPTER 2

Sensitivity, Selectivity, and

Stability of Gas-Sensitive
Metal-Oxide
Nanostructures
V. E. Bochenkov, G. B. SergeeV
Laboratory of Low Temperature Chemistry, Department of
Chemistry, M. V. Lomonosov Moscow State University, Moscow
119991, Russia

CONTENTS 1.Introduction32
1.1.DefinitionandClassification321.2.CharacteristicsofGasSensors33
2. Metal-Oxid e Gas Sensors 3 4 2.1. Historica l Backgroun d 3 4 2.2. Structur e of the Sensing Layer 3 4 2.3.
The Nature of Gas Sensitivit y in Semiconducto r
Metal Oxide Nanomaterial s 3 5 2.4. Factor s Affectin g the Sensitivit y of MetalOxid e
GasSensorMaterials372.5.Selectivity402.6.StabilityofMetalOxideGasSensors41
3.PropertiesandApplicationsofNanostructuredMetalOxides423.1.DetectionofHydrocarbons423.2.Detectionof
Alcohols433.3.DetectionofCarbonOxides443.4.DetectionofNitrogenOxides453.5.DetectionofHydrogen463.6.
DetectionofAmmonia473.7.DetectionofOtherGases48
4. Conclusion s and Future Direction s 4 8 Reference s 4 8

ISBN: 1-58883-176-0 Mclal Oxide Nniuvlnictinv* and Yheir Applications Copyright 2010 by American Scientific Publishers
Hchted by Ahmod Um.ir and Yoon-Bong llahn
All rights of reproduction in any form reserved. Volume 3: Pages 31-52

3
132Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures

1. INTRODUCTION 1.1.
Definition and Classification
Accordingto thedefinition ofa gas sensor,given bytheInternational Union of Pure andAppliedChemistry(lUPAC), "a chemical sensoris a
devicethat transforms chemical information, ranging from theconcentration of aspecificsamplecomponent tototal compositionanalysis, into
an analyticallyuseful signal.Thechemical information, mentioned above, mayoriginatefrom a chemical reactionoftheanalyte or from a
physical propertyofthesystem investigated" [1].Typically,chemical sensors consist oftwomainparts,a receptor and a transducer. The
receptor transforms chemical information into a form ofenergy,which can bemeasuredbythe transducer.Thetransducer converts this energy
intoauseful, typicallyelectrical, analytical signal.

Chemicalsensorsareclassifiedinanumberofdifferentways.Oneoftheclassificationsusestheoperatingprincipleofthereceptor[1].Usingthis
principle,onecandistinguishbetween
physical sensors, chemical
sensors, and biochemical
sensors.
In physical sensors no chemical reaction takes place at the receptor, and the signal is a result of a physical process, such as mass,
absorbance, refractive index, temperature, or conductivity change. Chemical sensors are based on chemical reactions between
analyte molecules and the receptor. Biochemical sensors are a subclass of chemical sensors, where the reaction is biochemical.
Typical examples of such sensors are microbial potentiometric sensors or immunosensors. It is not alway s possible to discriminate
between physical and chemical sensors. Agood example is a gas sensor, where the signal is a result of gas adsorption.
Chemicalsensorscanbeclassifiedaccordingtheoperatingprincipleofthetransducer.AnexampleofsuchclassificationispresentedinTable1.
Anumber of other classification schemes can be based on the type of sensitive material (e.g., metal-oxide, polymeric, and inorganic),
fabrication technology(e.g., screen-printed and vapor deposited), field of application (automotive, medicine, and environmental), and so
on.This chapter mainlydiscusses the features of metal-oxide gas sensors and
Table1. Classificationofchemicalsensorsbytransduceroperatingprinciple.
Transduceroperating'principleMeasuredpropertiesSourceofsignal
OpticalAbsorbanceKithercausedbyanalyteitself,orduetoreactionwithcertainindicator
FluorescenceChangesinfluorescencepropertiesluminescenceHmission,causedbychemicalreactionRefractiveindextor
example,causedbychangeinsolution
compositionScatteringCausedbyparticlesofdefinitesizepresentin
thesampleElectrochemicalVoltammetricChangeofcurrentismeasured.Forexample,chemically
inert,activeandmodifiedelectrodesPotentiometricChangeofelectrodepotentialismeasuredagainstareferenceelectrodeMassPiezoelectricChangesofresonantfrequencyofquartzoscillatorplate
duetoadsorptionof analyteonitschemicallymodifiedsurface
AcousticwaveChangesofpropagationvelocityofacousticwaveMagneticParamagneticForexample,oxygenmonitorsCalorimetricMeateffects
Changesoftemperatureduetoheateffectsofreaction
oradsorptio
nSensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures33

presents their sensing mechanisms. The main sensor characteristics and the approaches for their improvement are considered.
The modern results and future prospects of using nanotechnology with its ability to precisely control the structure of the sensitive
layers in order to affect sensor performance are reviewed.

1.2.CharacteristicsofGasSensors
In order to characterize sensor performance a set of parameters is used [2]. The most important parameters and their definitions are listed
below.
Sensitivity is a change of measured signal per analyte concentration unit, i.e., the slope of a calibration graph. This parameter is
sometimes confused with the detection limit.
Selectivity refers to characteristics that determine whether a sensor can respond selectively to a group of analytes or even
specifically to a single analyte.
Stability is theabilityofasensorto providereproducible results fora certainperiodof time.This includes retainingthesensitivity,
selectivity,response, and recoverytime.
Detection limit is the lowest concentration of the analyte that can be detected by the sensor under given conditions,
particularly at a given temperature.
Dynamic range is the analyte concentration range between the detection limit and the highest limiting
concentration.
Linearity is the relative deviation of an experimentally determined calibration graph from an ideal straight line.
Resolution is the lowest concentration difference that can be distinguished by sensor. Response time is the time required
for sensor to respond to a step concentration

change from zero to a certain concentration value. Recovery time is the time it takes for the sensor signal to return to its initial
value
after a step concentration change from a certain value to zero. Working temperature is usually the
temperature that corresponds to maximum
sensitivity. Hysteresis is the maximum difference in output when the value is approached with
an increasing and a decreasing analyte concentration range. Life cycle is the period of time over which the
sensor will continuously operate.
All of these parameters are used to characterize the properties of a particular material or device. An ideal chemical sensor would
posses s high sensitivity,dynamic range, selectivity and stability; low detection limit; good linearity; small hysteresis and response time;
and long life cycle. Investigators usually make efforts to approach only some of these ideal characteristics, disregarding the others. On
one hand, this is because the task of creating an ideal sensor for some gases is extremely difficult, if at all possible. On the other hand, real
applications usually do not require sensors with all perfect characteristics at once. For example, a sensor device monitoring the
concentration of a component in industrial process does not need a detection limit at the ppb level, though the response time at range of
seconds or less would be desirable. In case of environmental monitoring applications, when the concentrations of pollutants normally
change slowly , the detection limit requirements can be much higher, but response time of a few minutes can be acceptable.
Thefirstsectionofthischapterisdevotedtothedefinitionandclassificationofgassensors,andadiscussionoffactorsaffectingthesensitivityandselectivity
ofmetal-oxidebasedsensors.Attentionispaidtothestructureandconductivityofthesurfacelayer,thesize-andshape-dependenceofthesensitivityofthe
oxideparticles,andtheinfluenceofdopingongassensorcharacteristics.Thesecondsectiondiscussestheapplicationsofsuchmetal-oxidenanostructures
asSnO2,ZnO,andWO,andtheircombinationsforanalysisofhydrocarbons,toxicoxidesofcarbon,andnitrogenandfordetectionofalcoholsand
someothervolatileorganiccompounds
.34 Sensitivity,Selectivity,and Stability of Gas-Sensitive Metal-Oxide Nanostructures

2. METAL-OXIDE GAS SENSORS

2.1. Historical Background
It has been known for a long time that electrical resistance of a semiconductor is very sensitive to the presence of
impurities in its volume or at the surface. In 1953, this effect was demonstrated for Ge [3]. Later, it was shown that the
conductivity of ZnO thin films heated to ~300C was sensitive to the presence of traces of reactive gases in the air [4].
Similar properties were reported for SnO2, with higher stability [5]. These results initiated further development of
commercial gas sensors.
The early metal oxide-based sensor materials possessed a number of unpleasant characteristics, such as high
cross-sensitivity, sensitivity to humidity, long-term signal drift and, slow sensor response. In order to improve
sensor performance, a series of various metal-oxide semiconductors have been tested [6]. At first, the poor
understanding of sensor response mechanisms caused the use of trial and error strategy in the search of an
appropriate material. The most successful investigations were connected with SnO2, ZnO, and TiO2. Parallel to
this approach, the basic research of metal-oxide materials was carried out in scientific laboratories.
Several decades after the first published paper on SnO2 sensors, they became the bestunderstood
prototype of oxide-based gas sensors. It was well known that the sensor characteristics can be changed by
varying the crystal structure, dopants, preparation technology, operation temperature, etc. Nonetheless,
highly specific metal-oxide sensors were still not available. In recent years, the interest of researchers and
engineers to gassensitive materials has grown substantially due to the progress in nanotechnology. This
interest is primarily connected to the promising electronic properties of nanomaterials: their sizedependence and ability to control the material structure by new experimental techniques [7]. More and more
materials and devices are produced every year with-the use of nanotechnology [8-10].

2.2. Structure of the Sensing Layer

The typical metal-oxide gas sensor element consists of the following parts: sensitive layer,
substrate,
electrodes, and
heater.

Today,most of the commercial metal-oxide gas sensors are manufactured byscreen printing on small and thin ceramic
substrates. The ^advantage of this preparation technique is that the thick films of metal oxide semiconductor can be deposited in
batch processing, leading to small deviations of characteristics for different sensor elements.
Although this fabrication technology is well-established, it possesses a number of drawbacks and needs to be
improved. Primarily, the drawbacks are connected with the necessity to keep the thick metal oxide film at high
temperature. Due to this reason the power consumption of screen-printed sensors can be as high as 1 W [11],
which makes them unable to be used in battery-driven devices. Another technological problem is*the proper
mounting of the overall hot ceramic plate to ensure the good thermal isolation between the sensor element and
housing.
These problems have promoted the development of substrate technology and strong research in preparation of the
sensitive layer. One promising solution is the integration of a sensing layer in standard microelectronic processing,
which overcomes the difficulties of the screen-printed sensors. In this case, an oxide layer is deposited onto a thin
dielectric membrane of low thermal conductivity, which provides good thermal isolation between the substrate
and the heated area on the membrane. Such a construction allows the power consumption to be kept at very low
levels [11]. Moreover, the total size of single sensor elements is reduced, so that a minimal distance between
electrodes lying in the fim range can be achieved. It enables the integration of signal-processing electronics and/or
multiple sensor elements on the same substrate
.Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures35

2.3.TheNatureofGasSensitivityinSemiconductorMetalOxide
Nanomaterials
The chang e of electrica l propertie s of the metal-oxid e semiconducto r due to adsorptio n of gas molecule s is primaril y
connecte d with the chemisorptio n of oxygen . Molecula r oxyge n adsorb' s on the surfac e by trappin g an electro n from
the conductio n band of the semiconductor . At temperature s betwee n 100 and 500 C the ionize d molecula r (O2) and
atomi c (O~, O2~) forms can be presen t at the surfac e [12]. The molecula r form dominate s belo w 150C , wherea s
above this temperature , ionic specie s prevai l [13, 14]. The genera l reactio n equatio n can be writte n as:
^ Of

l s

e "

^ ^

O " ,

S )

(1

Here O2gas is an oxyge n molecul e in the ambien t atmospher e and e is an electro n tha t can reach the surface ,
overcomin g the electri c fiel d resultin g from negativ e chargin g of the surface . Their concentratio n is s. S denote s
unoccupie d chemisorptio n sites for oxygen , O^S) is the chemisorbe d oxyge n with a 1 or 2 for singl y or doubl y
ionize d for m and 0 = 1 or 2 for atomi c or molecula r form, respectively . The presenc e of charge d species on the
surfac e of a semiconducto r induce s band bendin g and formatio n of a depletio n layer [15, 16]. Dependin g on the
type of semiconducto r the concentratio n of charg e carrier s in the surfac e layer can be either increase d or
decreased . The space charg e laye r is describe d by the thicknes s Ls and surfac e potentia l (Vs) [17, 18].
The conductance dependenc e can be found followin g the derivatio n give n in Ref. [13]. The mass action law can be writte n
in the form:
*ads[SI?2 =*d [' (2)
Let us denote the total concentration of the ox yge n adsorption sites
(occupied and unoccupi ed) as [S,] , so that [Sf] = [S] + [O(S)]. B y definitio n
the surfac e coverag e is

(3)
Equation(2)can be tha n rewritten :
(1-0)fc ads<Pof= kdcj (4)

Sinc e electro n concentratio n .. and surfac e coverag e are related , an additiona l equatio n is neede d to
find the dependenc e of ns with partia l oxyge n pressure . One can use the electroneutralit y equatio n
combine d with the Poisso n equation .
The electroneutralit y principl e in the Schottk y approximatio n state s that the charg e in the depletio n
layer Ls unde r surfac e A equal s to the charg e capture d by surfac e A. The usual workin g temperatur e of
metal-oxid e sensor s is high enoug h to assum e that all donor s are ionized , so the ionize d dono r
concentratio n is equal to the bulk electro n density nh. Therefor e one can write the electroneutralit y equatio
n

and the Poisso n equatio n for energ y as follows :

j4 (6 )
az- , . Settin g
boundar y condition s to
^P ==L, = 0 (7
)b e n s i t i v i t y , b e l c c t i v i t y , a n d b t a b i l i t y o t d a s - b e n s i t i v e M e t a l - U x i d e
JManostructures
and (2)
)(2) = t\- + |-" " (2 - 2 (1 ) 2 (9 )

resultsinEq.(9):;-:./s " LC (8

whic h lead s to the dependenc e of ban d bending , give n tha t V E/q:

V{z) =

2ct{Z~Zo)2 (10 )

This genera l dependenc e allow s surfac e ban d bendin g (at z = 0):

V , = ^ - z l ( 1 1 )
By combinin g thi s equatio n wit h electroneutralit y equatio n [Eq . (5) ] and takin g int o accoun t the followin g relatio
n/, = //,, exp kT(12)
one obtain s Eq . (13) . In combinatio n wit h Eq. (4) it allow s determinatio n of , and as a functio n of oxyge n partia l
pressur e an d temperatur e eithe r numericall y or by usin g variou s approximations .
0 = -[St]-q2(13)
For granula r meta l oxides , the formatio n of a depletio n laye r at the surfac e of grain s and grai n boundarie s lead s to the
formatio n of Schottk y barrier s betwee n the oxid e crys tallites , as depicte d in Figur e 1. Th e densit y of surfac e oxyge n
ion s an d the heigh t and widt h of Schottk y barrier s depen d on the oxyge n partia l pressur e in the surroundin g
atmosphere . Th e electroni c theor y of adsorptio n [16 ] is in quantitativ e agreemen t wit h the experimentall y observe d
conductanc e dependencie s of semiconducto r layer s on oxyge n partia l pressur e [19] .
Dependin g on the content of the atmosphere , the concentratio n of the surfac e oxyge n ionsan d therefor e the
occupatio n of the surfac e states^ca n be changed , leadin g to the

VB
Figure1.Schematicrepresentationofbarrierformationatthegrainboundariesduetothespacechargelayer.Theshadedpartdenotesthespacechargeregion(high
resistivity);theun-shadedpartdenotesthecoreregion(lowresistivity).CBandVBarethelowestedgeoftheconductionbandandthehighestedgeofthevalenceband,
respectively
.Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostruetures37

changeinconductivity.Asameasureofgassensitivityonecanuseeithertheconductivitychangeofthesample,exposedtotheanalytecontainingatmosphereinrelationtoitsconductivityinthereferencegas,ortheslopeofthedependenceofconductivityonanalyte
concentration[20].

2.4. Factors Affecting the Sensitivity of Metal-Oxide Gas Sensor Materials

As mentioned above, the requirements for each gas sensor depend on the particular application. It is not necessary to
have material with a detection limit of one molecule if the sensor is designed to work in the 1-10% concentration
range. Nonetheless, materials with high sensitivity and low detection limit always attract the attention of scientists and
engineers. In this section, the main approaches for increasing the gas sensitivity of metal-oxide sensor materials are
listed, namely those utilizing the size effects and doping by metal or other metal oxides.

2.4.1. Size and Shape Effects

Since during the formation of a space charge layer the carrier concentration in volume is decreased onlyin thickness Ls, three
types of conductance mechanisms, as illustrated in Figure 2 can be realized. For large crystallites the grain size D 3> 2L, and
the conductance of the film is limited bySchottkybarriers at grain boundaries. In this case, the sensitivityis practically
independent of D. When grain size is comparable to 2L(D = 2L) everyconducting channel in the necks between grains
becomes small enough to influence the total conductivity.Since the number of necks is much larger the grain contacts, they
govern the conductivityof the material and define the size-dependence of gas sensitivity.If D < 2L, everygrain is fully
involved in the space charge layer, and the electron transport i*"affected bythe charge on the particles' surfaces.
TheconsideredSchottkybarrier formationmodel wasdevelopedforthesemi-infiniteplanargeometrysystem. Itcanbesafely
usedtodescribethebarrierformationincaseof largemetal-oxidegrains.However,formaterialswiththegrainsizescomparableto
thelengthofthedepletionregion, theeffectofthecurvaturecannotbeneglected,sincethedensityofsurfacestatesdependsonthe
grainradius[21, 22].
The shape of a bottom of conductive band for the grains of different size was studied theoretically.Application of the
depletion approximation (DA) under spherical symmetryallowed the calculation of an an analytical solution for the potential
P(r) = (Ech(r))/q, where n,(r) is the energyof the bottom of of the conductive band at a distance r from the center of a grain.
For a more general case, where DAis not applicable, the Poisson equation using a complete expression for the charge density
can be solved onlynumerically.The calculated potential shape inside the grains agrees with the experimentallyobserved
flattening of the band bending for films in air [21, 23]. Thus, byreducing the

(b)

(c)

Figure2. Threemechanismsofconductanceinmetal-oxidegas-sensitivematerials.Theshadedpartshowsthespacechargeregion(highresistivity),whiletheun-shadedpartshowsthe
coreregion(lowresistivity),(a)D<2L,grainboundarycontrol;(b) D<2L, neckcontrol;(c)D<2/.,graincontrol

.38Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures

particle size the conduction of the sample may be controlled by the grain boundaries, necks, or grains. The latter case is the most
desirable, since it allows achieving the highest resistance change. For different semiconductor oxides the length of depletion layer
may vary in the range of 1-100 nm. Numerous experimental investigations of nanostructured metal-oxide films revealed a strong
increase in sensitivity when the average grain size was reduced to several nanometers [5, 24-27]. Systematic analysis of sizedependence of SnO2 sensitivity was presented recently [28].
Another prospective approach is to affect the sensitivity by changing the microstructure and porosity. For this purpose the
low-temperature vapor co-deposition of metal and inert gas can be used. After removing the gas by annealing, the highly
porous metal structure can be formed. Then, metal can be oxidized by reaction with oxygen. This approach was used for
preparation of porous Pb/PbO nanostructures by co-deposition of Pb vapors with CO2 at 80 followed by annealing [29].
SnO2 and TiO2 mesoporous powders fabricated using a self-assembl y of a surfactant followed by treatment with
phosphoric acid as well as conventional tin oxide powders with surfaces modified by mesoporous SnO2 show higher sensor
performance than corresponding metal-oxide powder materials, which have lower specific surface area [30, 31]. Other
porous metal oxides also exhibit increased gas sensitivity [32-34].
In recent years, a definite trend in using quasi one-dimensional (ID) nario-objects for gas sensor applications has been observed
[7, 35-39]. This is due partly to expanding opportunities for synthesis and characterization of such structures [40, 41]. Besides, the
application of nanowires, nanorods, nanobelts, and nanotubes for gas sensors can signif icantly lower the detection limit, since the
conductance of ID objects is affected by lower amounts of adsorbed analyte than is the case for thin granular films. It was found
that SnO2 nanowires are sensitive to low CO concentrations [42^14], so the gas sensitivity of SnO2 nanobelts (the quasi-lD
materials with defined crystal structure) to polluting gase s like CO, NO2, and ethanol was tested [35, 37, 45].
An additional increase of sensitivity can be achieved by creating ID objects with necks that define the conductivity of the whole
nano-object. The comparative study of the sensor response to 0.4 ppm of hydrogen of straight SnO2 nanowires with diameter of ~100
nm and segmented nanowires consisting of thick parts 500 nm in diameter connected by thin parts 10 nm in diameter [46] was carried
out. It was found that response is larger for segmented nanowires, despite the fact that their mean radius is almost three times larger than
that of straight nanowires.

2.4.2. Doping
Thesensitivityofmetal-oxidegas sensorscanbesubstantiallyimprovedbydispersingalowconcentrationofadditives,suchasPd[47,48],Pt
[49],Au[50,51],Ag[28,52,53],Cu[54],Co[55],andF[56]onoxidesurfaceorinitsvolume.Althoughdopinghasbeenusedforalongtime
nowinpreparationofcommercialgassensors,theworkingprincipleofadditive-modifiedmetal-oxidematerials isstillnotcompletely
understood.Two generalschemes ofthegassensingmechanismaredepictedinFigure3.In thechemicalscheme(Fig.3(a))thereactiontakes
placeattheoxidesurface.Theroleoftheadditivenanoparticles isconsideredwithinaspilloverprocess,increasingthemetal-oxide
(a) (h > ..

Figure3. Chemical(a)andelectronic(b)sensitizationschemesinmetal-dopedSnO,gassensor.Reprintedwithpermissionfrom|7],V.[:.BochenkovandG.B.Sergeev, Adv.Coll.Int.Sci. 116,245(2005).

2005,KlsevierLimited
.Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNarwstructures 39

surfacecoverageofthegas,involved inthesensingscheme.In theelectronicmechanism(Fig.3(b))thereactioninvolvesthedopantatoms,and

theoxidematerial hastotransduce the electrochemicalchangesintoadetectableoutputsignal.Moreover,theintroductionofadditivesmaylead
totheformationofnewdonororacceptorenergystates orinfluence the grain sizeandgrowthmechanism[57].
Thechemicalschemeisusuallyconsidered inthecaseofcatalyticadditives, forexamplePt-orPd-dopedSnO2 materialexposedto
hydrogen,hydrocarbons, orcarbonmonoxide[58-60].It issupposed thatthereductionofgasmolecules isfirstactivatedbythe metal surface,
formingtheactivesurfacespecies thatthen reactviaaspilloverprocesswiththechargedoxygenmolecules,adsorbedontinoxide.Thisreaction
leads tothere-injectionofthelocalized electrons back tothebulk,thusincreasingtheconductivityofthematerial.Forinstance,thesensing
mechanismproposed forthePt/SnO7 +COsysteminvolvestwomainprocesses [58].First,atelevatedtemperature,Ptisoxidizedbythe
chemisorbedoxygen:
2Oii l d s P t O 2
Second, exposure to CO leads to a reduction of platinum oxide:

(14)Pt+

P t O , + 2 C O - > P t + 2 C O , (15) The analysis of published papers on doped metal oxide gas sensors shows the increase

ofsuchworksinrecentyears.Theresultsofaliteraturesearchusingthewords"metaloxideANDgassensorANDdoped"intitle,keywords,and
abstractarepresentedinFigure4.
'ThoughthesearchcriteriadonotallowthevaluespresentedinFigure4tobeconsideredasprecisenumberofpapersusingdopedmetaloxide
materialsasgassensors,itgivessomeideasoftheexistingtrends.Dataonyear2007arenotincluded,since the informationaboutrecently
publishedpaperscouldbeunavailableatthemomentofpreparationofagivenmanuscript.Thevarietyofelementsusedfordopingthemetal
oxides,isnoteworthy.Thediagram,presentingtherelativecomparisonofdopants,usedforenhancingpropertiesofSnO2 gassensorsinrecent
years,isdepictedinFigure5
The most often used dopant for SnO7 gas sensors is palladium due to its well known catalytic properties.Asimilar situation is observed
for other metal-oxide gas sensors.Another popular doping element is copper.It was found that the dopingof SnO2 with Cu enhances the
sensitivityand selectivityto H2S [61-63]. The same effect was observed for CuO-SnO2 [64, 65] and SnO2-CuO-SnO2 [66]
heterostructures.This phenomenon i
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40 Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures
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explained by the decreasing barrier height in p-CuO--SnO2 due to the chemical transformation of highly resistiv e CuO
into good-conducting Cu2S. Thorough studies have shown that the copper atoms in Cu-doped SnO2 can form donor-like
sites, which possess much better stability than the intrinsic donors (oxygen vacancies) in pure SnO2 [67]. Doping by metal
nanoparticles affects not only the sensitivity, but also the selectivity of the metal-oxide gas sensors.

2.5.Selectivity
One of the main challenges to the developers of metal-oxide gas sensors is high selectivity. Currently, two general approaches exist
for enhancing the selective properties of sensors. The first one is aimed at preparing a materfal that is specifically sensitive to one
compound and has low or zero cross-sensitivity to other compounds that may be present in the working atmosphere. To do this, the
optimal temperature, doping elements, and their concentrations are investigated. Nonetheless, it is usually very difficult to achieve an
absolutely selective metal oxide gas sensor in practice, and most of the materials posses s cross-sensitivity at least to humidity and
other vapors or gases .
Anotherapproach is based on thepreparation ofmaterials fordiscriminationbetween several analytes inamixture.It is impossibletodothis
byusingone sensorsignal; therefore, it is usuallydoneeither bymodulation ofsensortemperature[68-74] orbyusingsensor arrays [75-77].In
theformer case, such discrimination is possiblebecause ofthedifferent adsorptionandreactivityproperties ofanalytes.In the lattercase,N
signals areobtained simultaneouslyfrom Nsensors, which usuallydifferin some way(e.g.,dopingelement, dopingratio,grainsize, or
temperature).Thesekind ofdevices areusuallyreferred to as "electronicnoses."In bothcases,signal s aretypicallyanalyzedbyan artificial
neural network.

2.5.1. Modulation of Temperature

Typically, temperature dependence of a metal-oxide sensor signal to the presence of a given analyte possesse s a bell shape with a
maximum at a certain temperature [78]
.Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNnnostructures41

This dependence arises due to several reasons. First of all, as mentioned above, the charge of oxygen species
adsorbed at the oxide's surface depends on temperature [12]. Second, since the oxidation reaction is an activated
process, its rate increases with temperature. Finally, all adsorption, desorption, and diffusion processes are
temperaturedependent [79]. Thus, temperature modulation leads to response patterns that are characteristic of the
species present in a gas mixture [80]. This allows measuring of multivariate information from every single sensor. An
appropriate extraction of this information helps improve selectivity [81]. For example, a dynamic measurement
method for the rapid identification and determination of volatile organic compounds (VOCs) in ambient air using a
single SnO2-based gas sensor was developed [73]. The sensor operated in a rectangular temperature-modulation
mode. The working temperature of the sensor was modulated between 250 and 300C. It was shown that the
discrete wavelet transform allows important features to be extracted from the sensor response. These features can
then be processed using a pattern recognition algorithm. The species considered can be discriminated with a 100%
success rate using a back propagation network, and the concentrations of the organic vapors can also be accurately
predicted.
Nonlinear responses of SnO2 sensors to alcohol vapors and hydrocarbons were found to depend characteristically on
the scanning profile of the cyclic temperature change [70]. This allowed an increase in the selectivity to target analytes.
The temperature was regulated by the second-harmonic heater voltage to improve the discrimination of the nonlinear
dynamic response. The phase of the second-harmonic heater voltage can partially change the dynamic sensor response,
which depends on the kinetics of gases on the sensor surface. The dynamic responses of a semiconductor gas sensor
under the application of a temperature variation including the second harmonic were characterized by the higher
harmonics of fast Fourier transformation (FFT).
SmalltemperaturevariationsofananoparticularSnO2 gassensorwerereportedtoallowdifferentiationbetweendifferentgasmixtures
atappmlevel[69].Thus,differentconcentrationsofCO(from50to200ppm)werewelldifferentiatedevenathighC3HX
andNO2 concentrations.Itwasshownthattheshapesoftransientresponsescanbemodifiedbyaddingdifferentcatalysts(Pt,Pd)inan
SnCXsensinglayer.
2.5.2. Sensor Arrays The sensor arrays are named "electronic noses" due to the parallel between
the measurement concept of the instrument and that of the mammalian olfactory system. In the latter, during sniffing, the volatile
compounds reach the receptors located in the upper nasal cavity. Electrical stimuli produced by the receptors are transmitted
by neurons to the brain, where the -pattern recognition process takes place with the help of memory. Electronic noses
operate using a similar principle: the signals from different semi-selective sensors form signals, which are then analyzed by
an artificial neural network program. Similar aromas generally result in similar sensor response patterns. Many approaches
exist for making the array elements in a single sensor possess different sensitivities to various analytes, including doping with
different chemical elements [82, 83], formation of grains using various mixed oxides [84], and applying the temperature
gradient over the sensor array [76, 85]. The current status of the development of electronic nose systems was reviewed
recently [77, 86].

2.6.StabilityofMetalOxideGasSensors
Anotherissueofmetal-oxidegassensormaterialsistheirlowstabilityandlong-rangesignaldrift.Thisproblemleadstoinuncertain
results,falsealarmsandtheneedtofrequentlyrecalibrateorreplacesensors.Littleattentionispaidintheliteraturetotheproblemsof
stability.Onlyafewpapers,citedinthischapter,reportthestabilityofsensorresponseinaperiodofseveraldays[87].
Generally,nanostructuredoxideswithsmall grainsas well as nanotubes, nanorods etc. are subject todegradation because of
their high reactivity.Thereisnounified approachtoincreasingthestabilityof metal-oxidegas sensors. Tosome extent, stability
canb
e42Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures
increased by calcination and annealing as the post-processing treatment and by reducing the working temperature of the sensor
element. Doping metal oxides with metal particles or carbon nanotubes as well as synthesis of mixed oxides have been also reported to
increase the stability of sensor elements [88, 89].

One can distinguish between the two types of sensor stability. One is connected with reproclucibility of sensor characteristics
during a certain period of time at working conditions, which may include high temperature and the presence of a known analyte.
Such stability may be referred to as active stability. Another type of sensor stability, which can be called conservative stability, is
connected with retaining the sensitivity and selectivity during a period of time at normal storage conditions, such as room
temperature and ambient humidity.

3. PROPERTIES AND APPLICATIONS OF

NANOSTRUCTURED METAL OXIDES
In this section, more concrete examples of metal-oxide sensor development will be presented. The material is subdivided by target
analyte compounds, discussing sensors for hydrocarbons, alcohols, carbon oxides, nitrogen oxides, hydrogen, ammonia and other
gases. Each subsection contains a table citing some of the recent papers with indication of the sensor material, working temperature,
and the analyte and concentration that are detectable by given sensors. It can be as the detection limit, so as the dynamic range or just
tine concentration used by authors to measure the sensitivity of synthesized material. Since the various types of metal-oxide gas
sensors and their applications for detection of various gase s and volatile organic compounds are numerous, we will discuss only
some examples that are notable from our point of view .

3.1. Detection of Hydrocarbons

In recent years, metal oxides have been widelyused for analysis of hydrocarbons. Sensors for some aliphatic and aromatic hydrocarbons
have been developed, and attention has been paid to the detection of volatile liquid as well as gaseous compounds. Some recentworks on
hydrocarbons sensors are presented in Table 2.
Theapplicationofmetaloxidestothedetectionofhydrocarbonsisreviewedhereusingtheexampleofmethane,thefirstmemberofthealiphaticrow.
Methaneiswidespreadinnatureandformsexplosivemixtureswithair.Therefore,thedevelopmentofcheapgassensorsfordetectionofmethaneand
smallhydrocarbonsisanimportantproblem.
Theapplicationofthinzincoxidefilmswithcontactsmadeofnoblemetalsfordetectionofmethaneisdescribedinpapers[95,98].ThinnanocrystallinefilmsofZnO
weredepositedona0.6/xm-thickSiOi-coatedp-Sisubstratebyasol-gelmethod.ThethicknessofZnOfilmswasabout900ran.Thecontactsofdifferentmetals(Pd-Ag,
Rh,andPt)weredepositedusingane-beamevaporator.Theshortestresponsetime(16s)wasfoundforPcl-Agcontacts,whilethemaximumresponsevalue(84%)was
observedincaseofRhcontactsat250C.
Table2. Somerecentworks on detectionofhydrocarbons
.
S nO ,: W
Materi
O ; Analyt
al ZnO
e
ZnO:AI
C-H,,
ZnO:
ZnO
SnO,
ZnO
ZnO
II,
,

1
thvleneC o n c e n
tration
0-200 ppm
5,000 ppm
1,000 ppm
1,000 ppm
500-10,00 0
ppm 0.5-1%

0.1-1".. 2-cS
ppmTemperat
ure (C) 600
350 Room
t e mp .

3
0
0
3
5
0
5
03
5
0
3
03
5
0
3
0
0
K
ef.
[90][91]
[42](43]
[94]
[45|
[%]
[97

]Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostruetures43

Aproposedmechanismofsensorresponseinvolvesdissociationofmethanetoamethyl groupandahydrogenatomfollowedby
recombinationofhydrogenatoms:
(fr) ULK)

+ H(lds) (16) 2H(ads) ^ H2(fr,, (17)

The formed hydrogen molecule then reacts with adsorbed oxygen,

producing H2O and releasing trapped electrons to the conduction
band of metal oxide semiconductor |99].

3.2.DetectionofAlcohols
Sensormaterialsfordetectionofalcohols,especiallyethanol,arebeingactivelydeveloped.Theinterestinethanolisconnectedwithitswide
applicationinchemistry,medicine,andthefoodindustry.Precisequantitativedetectionofethanolvaporsisrequiredfordeterminationofquality
ofwinesandhumanhealth.Metaloxidesarewidelyusedfordetectionofethanol.Ethanolsensorsarebeingenhanced,andasisthecasefor
otheranalytes,theproblemsofsensitivity,selectivity,andstabilityarebeingaddressed.Someofthemostrecentpapersondetectionofalcohols
arepresentedinTable3.
ThemostwidelyusedmetaloxidematerialsforalcoholdetectionareSnCK,ZnO,WO,,TiO2 andZr2O3.Asarule,theanalysisis
carriedoutattemperaturesabove400"C;thereforeoneimportanttaskistodecreasetheoperatingtemperature.Besidetheconductivity
measurementsforsensordetectionofalcoholvaporsbymetaloxides,theoxidationprocesscanalsobeused.Oxidationofethanolmay
leadtoformationofacetaldehyde[118].Oxidationofaldehydeisaccompaniedbyphotoluminescence,whichisusedforquantitative
detectionofalcohol.
Chemiluminescencecausedbycatalyticoxidationofethanolvaporsonzincoxidehasbeenanalyzed[118].Oxidenanoparticles
weresynthesizedbyawetchemicalmethod"fromZnSO4 andNr^HCO^intheTritonX-100solutionfollowedbydryingat300C
andcalcinationat600C.TransmissionelectronmicroscopyshowedthatZnOparticlessizeswereinrangeof30-50nm.ByusingXraypowderdiffractiondata,theparticlescrystalstructurewereattributedtothewurtzitetype.Thesensitivityanditsdependenceon
alcoholvaporflowrateandtemperatureaswellasselectivityandlifetimewereinvestigatedby.luminescencestudies.
The sensor dynamic range was found to be 1-100 ppm, and the detection limit was estimated as 0.7 ppm. The optimal
temperature for analysis was 358C, and the optima
2,500-5,000
Methan
170
lTable 3. Some recent Z nO ZnO Z nO
Material
ZnO
SnO,:Pt
ZnO ZnO
ZnO:C,a
SnO 2 :Pd
ZnO:AI ZnO
ZnO:Pd ZnO
SnO 2 :CeO,
SnO,/ZnO
ZnO:In ZnO
ZnO:CeO :

Z nO :Fe ,O ,, soot v\4>rks on

detection of alcoho
Analyte
lithanol
Fthanol
Fthanol
Fthanol
Fthanol
Ethanol
Fthanol
ithanol
ithanol
ithanol
ithanol
ithanol
ithanol
ithanol
Fthanol
lithanol
Ethanol

ol,
Fthanol
Propan
o l s.

Concentrat
ion ppb
range
50-200 ppm
500 ppb 50
ppm 50 ppm
4,000 ppm
400 ppm
29.7 ppm
25-250 ppm
25-250 200
ppm
200 ppm 13 ppm
125-250 ppm
100 ppm 0.5
ppm 0.5 ppm
10 ppm

p p m Temperature
(C) 350
200 400500 350 300
350 250
20400
400
250-450 300
32 400
320 400
400

20
Ret
.
100
|
101]102
103]
104]75]
105]106
107]108]
109]1101
111]112
113]114]
1151116|
11

744Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures

flow rate was 100 mL/min. High selectivity to 50 ppm of NH 3, N2, CO2, SO2, CC14, QHft
wasreported.Stabilityofcataluminescenceintensitymeasuredat460nmwasfoundtobestableaftersevendays,withRSD (n =7)ofabout3.5%.
Theanalysisofartificialsamplemixturesrevealedgoodreproducibilityandpractically100%recoveryofthesensor[118].

Since ZnO can be prepared in a form of quasi-lD structure, a number of recent studies have been devoted to such materials. Thus, the
influence of ZnO nanorod diameter on ethanol sensitivity was demonstrated [119]. Vertically-aligned nanorods with diameters 100,
200, 400, and 800 nm were prepared byreactive Zn vapor deposition in an oxygencontainingambience on Si(100) substrate. The
materials were exposed to air containing 100 ppm of ethanol at 100C. Response and recovery times were about 10 s. The proposed
sensing mechanism includes the chemisorption of oxygen and oxidation of the adsorbed ethanol molecule:
C2H5OH(.u1b) + 6O(;ds)= 2CO2(frls) + 3H2O(I1 + 6e
(18 )
The highest sensitivity was demonstrated on materials with the lowest ZnO nanorod diameter (100 nm). The authors suggeste d
the reason is the higher surface-to-volume ratio, which promotes the adsorption of oxygen and higher concentration of lattice
oxygen vacancies" It is noteworthy that the sensitivity of nanorods with diameters of 400 and 800 nm was practically equal.
Wewillbrieflyconsiderthemostinterestingpeculiaritiesofalcoholsensorspublishedinotherpaperswithoutdetailedanalysisofallofthem.
ResultssimilartothosediscussedaboveontheethanolsensitivityofZnOnanorodsensorhavebeenobtainedat350C[100].Aluminium-doped
thinZnOfilms,producedbyradiofrequencymagnetronsputtering,showedsensitivitytoof~20-400ppmofethanolat250C[105].
Palladium-doped ZnO nanoparticles, produced byflame spray pyrolysi s of'organometallic precursors and mixed into an organic
paste to form thick sensing films, were tested for detection of ethanol vapors in the 25-250 ppm range in dry air at 400C. Dependence of
sensitivityon Pd content [107] and film thickness [120] was studied. Pd content varied in the range of 0-5 mol%. The maximum
sensitivitywas found to correspond to'?
1mol%ofPd.Thethinnestsensingfilm(5 /) showedthehighestsensitivityand.thefastest(withinseconds)responsetime.
Alowerconcentrationofethanol wasdetected byCeO2-dopedZnOthinfilms,fabricatedusingthedip-coatingmethod[113].The
concentrationof100ppmwasdetected withsensitivityof~80at320Cbyfilmscontaining5%Ce.It wasstatedthat theadditionofCeto
ZnOmodified theparticlesizedistribution.
Highlyporousthree-dimensional(3D)networks ofinterconnected ZnOtetrapods,havinglegswithlengthofseveralmicrometers and
diameterinthe0.1-1 / range, werefoundtobesensitivetoethanolconcentrationsaslowas0.5ppm[114,115,121].Theresponsetime
wasabout 10sat 400C.Thematerial wassynthesized byheatingZnpowderinafurnaceatatemperatureof900Candreactionwithair
andwatervapor.Thecontentofwatervaporinairwasfound tocontroltheadherenceontothesubstrateandthemorphologyofthedeposited
layers.

3.3. Detection of Carbon Oxides

Developmentofgassensorsforthedetectionofcarbonmonoxideisanissueoftheday,sinceCOisoneofthemosttoxicgases,andbeingodorless,itcan
formundetectedbyincompletecombustionoffuelinindustryandinprivatehouses.COgas,whichiscontainedinautomobileexhaustalongwith
nitrogenoxides,isoneofthemainenvironmentalcontaminants,especiallyinlargecities.Anothercarbonoxide, CCT-,, isoneofthegreenhousegases,
whicharebelievedtoberesponsiblefortheglobalwarmingeffect.ThemainsourceofCO2 todayisthecombustionoffossilfuels.Thenumberofpapers
devotedtodevelopmentofnewCO-,sensormaterialsisrathersmall.SomerecentlydevelopedsensormaterialsforCOandCO2 arepresentedinTable4
alongwiththereferencestotheoriginalpapers
.S e n s i t i v i t y , S e l e c t i v i t y , a n d S t a b i l i t y o f G a s - S e n s i t i v e M e t a l - O x i d e N a n o s t r u c t u r e s 4 5
Tab l e 4 . S o m e r e c e n t p a p e r s o n d e t e c t i o n
. Material
Sn
O2:
SnO 2 /TiO,:Nb
Pt
ZnO ZnO
Zn
ZnO:Cu, Cr
OA
ZnO SnO 2 :Au
nal
SnO 2
yte
CO

of carbon oxides
CO CO
CO CO
CO CO
CO
CO,Conc
entra tio
n
1,000 ppm
250 ppm
300 ppm
100 ppm

50-1,000 ppm
10 ppm 5 ppm
5 ppm
100%Temp e r a
ture ("O
658-680
400350
200, 300 250

2
5
0
3
0
0
2
4
5
4
0
0
1
3
0
R

et".

[122] [91]
[123]

[124] [125]

[12ft] [441
[127] [128

]DevelopmentofnewZnO-basedsensormaterialsforCOdetectiondealswith preparation ofnewformsofoxide.IDnanostructurearrayswiththeshapes

ofnanowires, nanonails, andnanotreeshavebeenpreparedbyoxygen-assistedthermalevaporationof metallic zinconquartzsubstrates[129].Theauthors

suggestedthattheformationofIDnanostructuresisgovernedbyaself-catalyzedvapor-liquid-solidapproach.ThesensitivityofthismaterialtoCOwas
studied;bymonitoringthechangeofitsresistancein the temperaturerange27-317C.Itwasfoundthatwhenthefilmisexposedto200ppm of COat225C,
itsresistancedecreasesbyafactorof~1.7.Responseandrecovery times areafewminutes.SensorresponseissuggestedtobebasedontheCOoxidation
reaction :

2CO+ O2 =2CO2 + e(19) i-Sensors based onnanonails andnanotrees are not specific.Theyreact to 200 ppm of
NO2 at225C,andto100ppmofH,Sat100C[129].TheinfluenceoftemperatureonCOsensitivitywasstudiedonanexampleofCu-dopedZnOthinfilms[53].The
films were vacuum-depositedonglasssubstratesatatemperatureof150C.

3.4.DetectionofNitrogenOxides
Large amountsofnitrogenoxidesareproducedbymotorvehicles.Othersourcesare electric Utilitiesandotherindustrial,commercial,andresidentialsourcesthat
burnfuels. The needforNOV sensordevelopmentisexplainedbyenvironmentalfactors.TheNOj gases cancausevariousproblemssuchassmogandacid
rain.Thus,sensorsareneeded for environmentalmonitoringandforuseincarstocontrolthecombustionprocess. Several recentexamplesofdevelopmentof
newsensormaterialstodetectnitrogenoxides are presentedinTable5.
The NO,sensorsforautomotiveapplicationsshoulddetectlevelsofNOinrangeof 100-2,000 ppmandNO,intherangeof20-200ppminthepresenceof1-10%
ofO2 attemperatures~400Corabove.Thus,theproblemsofsensitivity,selectivity,andstability must beaddressedwhendevelopingsuchmaterials.
Tabl e 5. Some recent papers on detection of nitrogen oxides
.Material ZnO
ZnO ZnO
NO,, NO,
SnO^WO,
SnO 2/SWCN
NO, NO,
ZnO:In
T SnO 2:Zn
N O , Concent
ZnO:Al
ration
ZnO:In 2 O,/W
O,
WO 2 /TiO,:Pt
Analvte
NO
N O ,
N O ,
N O ,
N O ,
N O ,

1000 ppm 500

ppm 5 ppm 1
ppm 1 ppm 560 ppm 0.1-5
ppm 20 ppm 10
ppm 10-570
ppmT e m p e r a t
ure (C) 200
150275

3
0
0
3
.
5
0
3
0
0
1
5
0
1
0
0
5
0
0
1
0
0
1
5
0
5
7
0
R
e
t
.

[41] 11301
[131] [132]
[133] [134] |
]46Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures

135] [136] [137]

[138

3.5. Detectionof Hydrogen

Analytical and sensor detection of hydrogen is of practical importance. On one hand, this is due to the increasing use of hydrogen as an
ecologicallyclean fuel. On the other hand, it is well known that mixtures of hydrogen and oxygen are explosive. Hydrogen leaks must be
carefullycontrolled in nuclear power plants and in the chemical industry.
Metal oxides, and particularly ZnO, are used for hydrogen detection. Some recent papers are presented in Table 6. Two
successful research directions are being developed. One is connected with using oxides doped with metal particles, which posses s
catalytic properties for hydrogenation reactions. Palladium and platinum metals are the most often used metals. Another direction is
connected with modification of oxides prepared by various methods. Acombination of these approaches is also used.
Thesensitivitytohydrogenofundopedand Pd-doped zincoxidenanorodswerecompredandtheresults,obtainedonZnOthinfilms,were
reported[144].Thesensitivitywasmeasured bytheresistancechangeatroom temperatureinthehydrogenconcentrationrange10-500ppm.
Hydrogenwasmixedwithair,and itwasfound thattheintheabsenceofPel,ZnOpossesseslowsensitivityto.Dopingbysputter-deposited
Pdclusters can increasethesensitivityofmaterialbyapproximatelyafactoroffive.Thisfactisexplainedbypromotingthecatalyticdissociation
ofhydrogen. Noresponsewasdetectedtothepresenceof O2 inambient air.Theresponsetimewasgreaterthan15min,butrecoverywas rapid
(lessthan20s).
ThesensitivitiesfordetectinghydrogenwithPt-coatedsingleZnOnanorodsandthinfilmsofvariousthicknesses(20-350nm)werecompared.It
wasfoundthattheresponseofPt-coatedsingleZnOnanorodsisapproximatelyafactorofthreelargeruponexposureto500ppmofH2 inN-,than
thatofzincoxidethinfilmsatroomtemperature.Thepowerconsumptionofbothtypesofsensorscanbeverylow.Thenanorodsensorsexhibitfaster
responsebutslowerrecoverythantheZnOthinfilms,whichisconsistentwithrelativelyhigheradsorptionabilityatthenanorod'ssurface.Thepoorer
currentstabilityofsinglenanorodsensordevicesincomparisonwithmultiplenanorodsensorsIsreported.
Highhydrogensensitivitywasdemonstratedonvertically-alignedZnOnanorods,synthesizedbyhydrothermi.iltechniqueat90ConaSi(100)
substrate[145].Thesensitivityofmaterialwasinvestigatedatroomtemperatureanddryairatatotalflowrateof500seem.ThediameterofZnO
nanorodsvariedfrom20to100nmandthelengthwasseveralhundredsnanometers.Hydrogenconcentrationsinrange20-200ppmwereused.The
sizeeffectoftheZnOnanorodsongassensingpropertieswerestudiedbycomparisonwithnanorodsof500nmindiameter.Itwasfoundthatfor
detectionof200ppmofhydrogenat250Cthesensitivityofnarrownamorodswasapproximatelyfourtimeslargerthanthesensitivityof500nm
diameternanorodsachievedat350C.Responsetimewas800sandrecoverytimewas200s.Itisreportedthatthesensitivityofthedevicecanbe
empiricallyrepresentedas S= 1+,(,)^,where P isthetargetgaspartialpressure,whichisproportionaltogasconcentration, A^ isaprefactorand
(3 istheexponenton P. Thevalueof fi isderivedfromthesurfaceinteractionbetweenchemisorbedoxygenanionsandreducinggasanditshould
becloseto0.5foruniformandorderedstructures[145].
T ab l e b . S o m e r e c e n t p a p e r s o n d e t e c t i o n o f h y d r o g e n
.Material
II.
SnO,:
1 1 , Concent
l ' d Anal
ZnO
ration 0.06,
ytei1,
SnO,:l'
,
II,
d
II,
0.50"''.. 1,000
S n O , : P d
II,
ppm 10-2,50 0
Z n O Z n O
ppm
H,
S n O , : F
H,
S n O , - A g ? O l ' t O ,

30
0
35
0
20
32
0
12
5
15
0
Ref
.

250 ppm 100

ppm 100 ppm 1
p p m Temperature
(C)
300-400 Room
t e mp . ,

[132]
[139]
[140]
[103]
[141]
[142]
[110]
[143
]Sensitivity , Selectivity , and Stabilit y of Gas-Sensitiv e Metal-Oxid e Nanostructure s 4 7
Tab l e 7. S ome r e c e n t pa pe r s on de t e c t i on of a mm oni a
.M a t e r i a l
ZnO
CdS ZnO
Sn0,:M
S n O 2 / M W C
ZnO:Cr,O,
SnO2:Pd
oOv,Fe
N T
ZnO:ZnS,
SnO2/S WCNT
: O ,

ZnO
WO,!
TiA n

a l v t e N H ,
N H , N H ,
N 1 1 , N H ,
N H , N H ,
N

N H ,
N H ,
C o n c
e n t r
a t i o
n
6 0 8 0 0
p p m
500
ppm
401,000
ppm
300
ppm
30
ppm
10-

500
100
10
10

ppm
ppm
ppm
ppm

5 - 4 0 0
p p m Tempera
ture ("C)
Room temp.
350
900
20
20
20

300-500
Room
temp.

3.6.DetectionofAmmonia

17
0
20
0R

ef.
|
14
8]

I l W l
|150]
|151|
[152]
|
I 4 4
|

|153]
|154]
[ 116 ]
| 1 5

Ammoniaisatoxicgasthatisnaturallypresentintheatmosphereinsub-ppblevels.However,muchlargerconcentrationscanbe
detectednearfarmswithdomesticanimals.Alargeamountofammoniaisprodacedbythechemicalindustryfortheproductionof
fertilizersorforuseinrefrigerationsystems.Ammoniasensorsareneededfortheearlydetectionofpossibleleakagesfromsuchsystems.
Anotherfieldofapplicationismedicine,sincetheincreaseofamountofammoniacontainedinexhaledaircanbeconnectedwithcertain
diseases,includingkidneydisorders[146]andulcerscausedby Hclicobactcrpylori. Acomprehensivereviewondifferenttypesofammonia
sensorshasbeenpublishedelsewhere[147].SeveralofthelatestresultsarepresentedinTable7.
Remarkable results are obtained on systems, including SnO, with single wall carbon -nanotubes (SWCNTs) or
multi-wall carbon nanotubes (MWCNTs), which allow detection
oflowconcentrationsofammoniaatroomtemperature.SystematicinvestigationsofdopingWO3 with48differentmetalshavebeencarriedout
[156,157].Fordoping,1wt%ofeachadditivewasused.ThebestincreaseofsensitivitytoammoniawasobservedforEr-andGa-dopedWO,
material.InanotherworkaparticularlygoodresponsetoammoniawasobservedforCr-dopedWO3 sensor[153].
Table 8. S ome recent pape rs on detection of othe r ga se s and VOCs
. Material
I,PC
SO,
ZnO ZnO
SnO,
TolueneC o n
ZnO ZnO
c e n t r a t i o n
S n O , Z nO
SnO,:Ni
S n O , : I 'd
ZnO:Pd
1ppm1ppb10ppm
ZnO
SnO,:Sr
200ppm10ppm20
SnO,:V
SnO,:La,O,
SnO2:CuO
ppm12ppm
ZnO ZnO
,
SnO,:CuO
100-300ppm10ppm1ppm
WO,A n a l
SnO,:Ag
0.01ppm
vte
ZnO
ppb
(C\H-,),
0.4%
N
0.2";. 0.2";.
( C , H , )
600 ppm
, N
10",.
( C H , ) ,
N
A c e t o n
e
A c e t o n
e
C \ H , O
H,S H,S
H2S H,S
11,S H,S
LI'C I,
PC,
LPC,
[,PG
LPG

1
0
p
p
m
5
p
p
m
3
0
p
p
m
T
e
m
p
e
r
a
t
u
r
e
(
"
C

)
350
150
170
400
170

Roo
m
temp
.

250-300
300

Room
temp.

7
0
1
5
0
2

0
57
8
40
0
40
0
35
0
17
0

210300

350
1 7 5 Ret.

172

158;
159]116]
160] 116] 161]

1331162]
163

I64j165]100]166][32]167]
168 169

170] I71|

]48Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostructures

3.7.DetectionofOtherGases
The remarkable results obtained recently for metal-oxide materials for detection of other toxic or flammable gase s and VOCs, such as
alkylamines, acetone, formaldehyde, hydrogen sulfide, liquified petroleum gas (LPG), sulfur dioxide and toluene are presented in Table 8.

4. CONCLUSIONS AND FUTURE DIRECTIONS

The considered applications and particular features of metal-oxide gas sensors allow us to formulate some general trends in this actively
developing field of science.
There is a clear tendency to search for new types of metal oxide nanostructures, includingnanowires, nanobelts, and nanorods that
promote the use of new synthetic techniques for preparation of novel sensor materials.
There has been an increase in the number of different dopants, particularly various metal and metal oxide
nanoparticles and substrate materials. These approaches are aimed at increasing the sensitivity and selectivity of metaloxide gas sensors.
Much effort is being madeto extend theworkingtemperature range ofmetal-oxidegas sensors andlower theoptimal working
temperature to 20-25C.Thegoal of theseinvestigations is to decreasethe power consumptionof sensorelements.
The analysis of available papers on sensor applications of metal-oxide nanostructures enables the formulation of a number of tasks that will
draw the main efforts of scientists and engineers working on gas sensing nanomaterials in near future.At the moment little attention has been
paid to the surface modification of sensor materials; hence, more efforts are needed on this topic. Moreover, the chemistry of metal and
metal oxide nanoparticles and their peculiarities and size effects have also been reviewed in recentlypublished books [173, 174]. However,
the reactivityof doped metal oxides is currentlyunder-investigated. The in situ spectroscopic studies of sensor materials at real working
conditions are still quite rear.
Detailed theoretical and experimental investigations are needed for deep understanding of possible physical and chemical
processes in real systems, involving metal oxides, dopants, analytes and various other molecules, such as water, which may be
present in the atmosphere in target applications. This understanding can help in solvin g the problems with sensitivity, selectivity,
and stability of sensor materials. One prospective approach is to chemically modify the surface of metal dopant particles with
appropriate ligands to increase the specificity of sensor.
Fromapracticalpointofview,theproblemofsensorstabilitydeservesmoreattentionthanithasnow.Itisalsonecessarytotesttherealsensor
workingconditionsforseveraldays.Higherstabilitywilldecreasethefrequencyoforcompletelyeliminatetheneedforverificationandrecalibrationofsensors.Anotherimportantproblemisthedevelopmentofsimplersensormaterialsandcheaperpreparationmethods.
Inouropinion,newperspectivesofusingmetaloxidesforgassensormaterialslienotonlyinthefieldofnewshapesanddecreaseofsizeof
basicelements,butalsointheapplicationofcompositesinvolvingmetaloxides,metals,andvariousorganicandinorganicligands.Creationofnew
sensitive,selective,andstablegassensormaterialsisoneofthemostimportantandactualtasksofnanochemistryandnanotechnology.

ACKNOWLEDGMENT S
ThefinancialsupportofRFBRgrant08-03-00712isacknowledged.

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