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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
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
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
2ct{Z~Zo)2 (10 )
VB
Figure1.Schematicrepresentationofbarrierformationatthegrainboundariesduetothespacechargelayer.Theshadedpartdenotesthespacechargeregion(high
resistivity);theun-shadedpartdenotesthecoreregion(lowresistivity).CBandVBarethelowestedgeoftheconductionbandandthehighestedgeofthevalenceband,
respectively
.Sensitivity,Selectivity,andStabilityofGas-SensitiveMetal-OxideNanostruetures37
changeinconductivity.Asameasureofgassensitivityonecanuseeithertheconductivitychangeofthesample,exposedtotheanalytecontainingatmosphereinrelationtoitsconductivityinthereferencegas,ortheslopeofthedependenceofconductivityonanalyte
concentration[20].
(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 > ..
(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
S b
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Ag
s " m e t a l
k e y w o r d s
o x i d e / '
.
Au
2 7 % 3
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%
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n Mo2O3
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3%
CO3O4
Fe 2 O 3
Ni
a P b
m Pd
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Si
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w o
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Figure 5.RelativecomparisonofdopantsforSnO,gassensors.
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.
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.
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)
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 :
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.
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
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 ,
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
[138
30
0
35
0
20
32
0
12
5
15
0
Ref
.
[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.
ACKNOWLEDGMENT S
ThefinancialsupportofRFBRgrant08-03-00712isacknowledged.
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