Sensors and Actuators, 10 (1986) 379 - 398 379

HUMIDITY SENSORS* PRINCIPLES AND APPLICATIONS

NOBORU YAMAZOE
Department of Materials Scrence and Technology, Gmduate School of Enganeenng
ScJences, Ky ushu Unwerwty 39, Kasuga, Fukuoka, 816 (Japan)
YASUHIRO SHIMIZU
Department of Materials Sczence and Engrneenng, Faculty of Engrneenng, Nagasaks
Unwerszty. Bunkyo-machr, Nagasakr, 852 (Japan)
(Received October 24, 1986,accepted October 31, 1986)

Abstract

In response to the strong demands for automatic control systems, many

kmds of humidity sensors based on humidity-sensitive electrical properties
have been mvestigated and placed on the market The humidity-sensitive
materials used are classified into three groups electrolytes, organic polymers
and porous ceramics This paper describes the principles, fabrication and
applications of the respective groups of humidity sensors, together with
recent topics including mmiaturlzatlon and mtegratlon of sensors

Introduction

Recent developments m automated systems have made ever-mcreasmg

demands for various kmds of physical and chemical sensors As humidity IS
a very common component in our environment, measurements and/or
control of humidity are important not only for human comfort but also for
a broad spectrum of industries and technologies Among the different types
of humidity sensors, those based on electrical properties such as impedance
(or resistance) and capacitance are best suited to modern automatic control
systems Generally speakmg, a humidity sensor has to fulfill the following
requirements to satisfy the widest range of apphcatlons (1) good sensitivity
m a wade humidity range, (2) quick response, (3) good reproducibility and
no hysteresis, (4) fitness to cuccuitry , (5) tough durability and long life,
(6) resistant to contammants, (7) mslgnificant dependence on temperature,
(8) simple structure and low cost
As shown m Table 1, the applications of humidity sensors are wlde-
spread, covering domestic electric apphances, automobiles, medical services,
various mdustnes and agriculture The purposes of adopting humidity
sensors and the operation conditions are quite different depending on the
field of application, each field requiring a specific humidity sensor In

0250-6874/86/$3 50 0 Elsevler Sequola/Prmted In The Netherlands

TABLE 1
Apphcatlons of humidity sensors

Apphcatlon Operatmg Temp Humidity range

(“Cl (%rh)

Domestic electric appliance Au condltlonmg system 5- 40 40- 70

Drier for clothing 80 o- 40
Microwave oven 5 - 100 2 -100
VTR* -5-60 60 - 100
Automobile Car wmdows* -20 - 80 50 - 100
Medlcal service Medical apparatus 10 - 30 80 - 100
Incubator 10 - 30 50 - 80
Industry Textile ml11(spinning) 10 - 30 50 - 100
Drier for ceramic powder 5 - 100 o- 50
Dehydrated food 50 -100 o- 50
Electric device manufacturing 5 -40 o- 50
Agriculture Forcing culture 5- 40 0 - 100
Measurement Thermo-hygrostatlc chamber -5 - 100 0 - 100
Radio-sonde -50 - 40 0 - 100
Hygrometer -5 - 100 0 -100

+Preventlon of dew condensation

 381

response to this situation, various kinds of humidity sensors have been

mvestlgated and developed, especially in Japan Although these sensors do
not always completely meet all the requirements mentioned above, many
have been put Into practical use Table 2 summarizes sensing materials,, prm-
ciples, operation temperatures, humidity ranges and response times for
important hunudlty sensors based on impedance or capacitance The sensmg
materials are roughly classified into three groups, z e , electrolytes, organic
polymers and porous ceramics In spite of the differences m matenals, most
sensors utihze a common phenomenon, that IS, physical adsorption (or
absorption) of water molecules Of course, chemical adsorption of water can
be also utlhzed, but Its apphcatlon 1s still confined to very special cases
The aim of the present paper 1s to descnbe the pnnclples and
apphcatlons of several types of humidity sensors so far developed Reference
will also be made to some recent advances m humidity sensors

2. Lithium chlonde hurm&ty sensor

An electnc hygrometer using hthlum chloride, developed by Dunmore

[ 11, operates on the pnnclple that hthmm chlonde solution immersed in a
porous binder changes Its lonlc conductlvlty depending on the relative
humldlty of the surrounding atomosphenc air [2 - 51
Figure 1 shows some vanatrons of this type A typical unit of a
Dunmore-type humldlty sensor IS shown m (a) An alumrmum tube coated
vvlth polystyrene resin 1s fitted with a pan of wound palladnnn wires
(electrodes), followed by a humidity-sensitive coating of partially hydrolysed
polyvinyl acetate Impregnated with hthlum chlonde The humidity range to
be covered by one unit 1s narrow, dependmg upon the amount of
impregnated hthmm chlonde For example, the humldlty-resistance
charactenstlcs A to E m Fig 2 are obtamed when the amounts of
impregnated hthlum chlonde are 0% (A), 0 25% (B), 0 5% (C), 1 0% (D) and
2 2% (E), respectively A wide relative humidity range from 10 to 100% can
be measured urlth a set of units with different sensing charactenstlcs A
small-sized, hghtwelght humidity sensor, 10 mm long, 4 mm wide, 0 2 mm
thick and 70 mg m weight has been made using plant pith as the porous
binder (Fig l(b)) [3,4] These sensors show rather slow responses to
humldlty but a fanly good stablhty, and have been widely used m
radio-sonde clrcmts as well as m mstruments for medical services Their use
m very humid envrronments should be avoided so as not to lower the
accuracy and hfe time
A dew indicator has been developed by using a hthlum chlonde
humidity sensor and a thermistor, as shown m fig l(c) [5] In this case, a
porous glass sheet 1s nnmersed m a hthmm chloride solution The thermistor
1s used to measure an equlllbrmm temperature, at which the water vapour
pressure of saturated hthlum chlonde solution becomes equal to that of the
surrounding air From the equlhbnum temperature, one can easily fmd the
TABLE 2
Charactelnstlcs of humldlty sensors

Type of matenal Principle Sensing element Operative range Response

time
Temp (“C) %r h

Electrolyte Impedance LICI + polyvmyl acetate -40 - 60 10 - 99 2- 5mm

(lomc) LlCl + pith -20 - 60 10 - 99 5 - 6mm
LlCl + glass flbre sheet -30 - 50 15 - 99 3 f 10 mm
Organic polymer Impedance (1) o- 40 0 - 100 2 mm
(lonlc) (2) -20 - 80 0 -100 5s
Impedance (3) -10 - 60 94 - 100 10 s
(electronic)
Capacitance Cellulose acetate -40 - 115 0 - 100 1s
Polylmlde 25 0 - 100 1 mm
Cellulose acetate buthyrate o- 50 0 - 100 30s
Porous ceramics Impedance MgCrzO‘j-T102 0 -150 1 - 100 10 s
(lomc) T10TV205 0 -150 15 - 100 10 s
ZnCr204--LiZnV04 0 -150 30 - 90 3 mm
Impedance Sr 1_,La,Sn03 300 - 500 l- lo* 2 mm
(electronic) ZrOzMgO 400 - 700 10 - lo* 10 s
Capacitance A1203 -10 - 40 1 - 100 10s
Ta20rMnOz -10 - 55 1 - 100 1 mm

(1) 2-hydroxy-3-methacryl-oxypropyl trlmethyl ammomum chloride + methacryhc ester

(2) Polystyrene sulphonate + vinyl polymer + N,N!methylene-bwacrylamlde
(3) Crosslmked hydrophilic acrylic polymer + carbon particles
*In ppm
 383

Q p Pd wire

/
Partially hydrolysed
polyvinyl acetate

pith lead wire

@I

insulator

hermlstor
metal tube
electrode

Fig 1 Various configurations of hthlum chloride humldlty sensors

Ei6
2
E
rl 5

E D C B A
4
0 20 40 60 80 100
Relative humldlty /%
Fig 2 Resistance-humidity characterlstlcs for several units of a Dunmore-type humldrty
sensor with different amounts of llthlum chlonde

the water vapour pressure and hence the dew pomt as well as the relative
humxdlty of the surrounding air

3. Polymer film hunudlty sensors

Although polymer film humrdlty sensors still remam modest m

practical apphcations compared urlth ceramic sensors, thev potentlahty has
been growing, especially m the field of sohd-state transducer technology
384

Polymer films are well suited to standard IC processing techniques to

fabncate a small, low cost sensor The sensors m this category can be
classlfled mto impedance and capacitance types, the impedance type being
further subdivided into ionic and electronic conduction types

3 1 Impedance-type humadlty sensors

A group of orgamc polymers having constrtuent loruc monomers such
as sodium stylenesulphonate exhibit loruc conductlvlty and are called
polymer electrolytes Their lonlc conductlvlty increases with an rncrease m
water adsorption, due to increases In the ionic moblhty and/or charge carrier
concentrations An Important problem encountered m adoptmg these
matenals to humidity sensors 1s water reslstlvlty Polymer electrolytes are
generally hydrophlhc and soluble m water, so that they have a poor
durablhty agamst water or dew condensation This problem has been
mitigated by crosshnkmg a hydrophlhc polymer wrth an appropriate cross-
lmkmg reagent and/or copolymenzmg hydrophlhc monomers with hydro-
phobic monomers
A thm-film humidity sensor, ‘Hument’, with a high accuracy (1%) was
developed m 1978 and has been placed on the market [ 61 A schematic view
of the sensor 1s shown in Fig 3 The thin humidity-sensltlve film 1s prepared
by copolymenzmg 2-hydroxy-3-methacryl oxypropyl tnmethyl ammonmm
chloride with metacryhc ester on an alumina substrate with patterned Au
electrodes of mterdlgtated form A porous polymer film covers the top of
the humldlty-sensitive film to protect it from contammatlon by oils, dust
and so on The electric resistance of the film, which takes a practical value
of less than 10’ above 30 - 40% r h , decreases exponentially as the relative
humidity increases, as shown in Fig 4 The response time 1s about 2 mm m
the adsorption process, while it IS a little longer m the desorptlon process
For adsorption-desorptlon cycles, this sensor exhibits extremely low
hystersls, mthm 1 0% r h
Many other copolymers have been investigated Examples are
crosslmked copolymers prepared from styrenesulphonate, a vinyl polymer
and N,N-methylene-bls-acrylamlde (a crosshnkmg regent) 17, 81, or from
styrenesulphonate and polyvmyl chloride [9], a copolymer of sodium
styrenesulphonate with 2-hydroxyethyl metacrylate [lo], and a graft
copolymer of tetrafluoroethylene with styrenesulphonate [ll] Sensltlvlty,
stability and rehablhty are of course dependent upon the chemrcal structure
of the polymers Irrespective of all these vanatlons, however, there IS a
common concept for deslgnmg polymeric films, I e , enhancement of the
water reslstlvlty by crosshnkmg or copolymenzatlon These mvestlgatlons
have provided useful mformatlon concerning response time and sensing
mechanism The response time 1s determined by the time it takes for water
vapour to diffuse into or out from a polymer film to reach an equlhbnum,
so that the film should be as thm as possible for quick responses Besides
the film thickness, an increase m hydrophoblclty of the constituent ionic
monomer appears to shorten the response time, while the mole fraction of
 0 63 mm

6.

2
$
- 5.

lead wire 4.
--!I

20 40 60 80 100
Relative humldlty /%
Fig 3 Schematic view of ‘Hument HPR’ type humldlty sensor
Fig 4 Resistance-humldlty characterlstlcs of the ‘Hument’ sensor at several temperatures

the constituent lomc monomer to non-lonlc monomer strongly affects the

sensing charactenstlcs [lo] At a fixed relative humldlty and temperature,
the electnc resistance decreases when the fraction of the constituent lomc
monomer mcreases It seems that the ion pours of the polymer electrolytes
are dlssoclated with water adsorption to liberate hydrated ions as dominant
charge carriers
An electronic conduction-type humidity sensor was developed m 1978
as a dew detector for the VTR cylmder [12] The sensor structure 1s very
sumlar to the one illustrated m Fig 3 The humldlty-sensltlve film m this
case 1s a crosslmked hydrophilic acryhc polymer m which carbon particles
are dispersed The swelhng of the polymer due to water absorption counter-
acts ohmic contacts between dispersed carbon particles and thus the elec-
tronic resistance of the film, which 1s measured with a d c voltage, increases
sharply as the relative humidity approaches loo%, as shown m Fig 5

3 2 Capacitance-type humldlty sensors

The relative permlttlvltles of polymers such as polylmldes and cellulose
acetates are known to range from 3 to 6, whereas pure water has a far larger
value of 78 54 at 25 “C It follows that the capacitance of polymers changes
sensltlvely with the absorption of water, and thus can be chosen as a
humldlty-sensitive property
A capacitive thm-film humidity sensor ‘Humlcape’, developed by
Vsusala m Finland, 1s now uldely used m radio-sonde and many other
humidity-measunng instruments [ 131 The sensor configuration 1s illustrated
m Fig 6 [14] Lower twm electrodes are attached on a glass substrate by
lndlum evaporation A humldlty-sensltlve matenal such as cellulose acetate
dlssolvmg ethylene dichloride 1s then apphed m a thm layer (about 1 pm
thick) On top of this gold ISevaporated as the upper electrode, which 1s thm
386

3
E
$
2
?
rl I Y

lower
1 electrode
(Au)
glass
substrat$+*~
0 20 40 60 80 100 fF
Relative humldlty /% 0,2 INIl
Fig 5 Resistance-humidity charactenstlcs of dew sensor

Fig 6 ConfiguratIon of ‘Hunucape’ humldlty sensor

(100 - 200 A) and porous enough to permit qLuck lateral moisture transport
The upper electrode acts as a common counter electrode to the lower twin
electrodes, and the composite capacitance of two bulk capacitors, which are
connected m senes with the upper electrode, 1s measured between the lower
twm electrodes This conflguratlon ehmmates dlfficultles m contactmg a lead
wire to the thin upper electrode As shown m Fig 7, the capacitance 1s
roughly proportional to the amblent humidity from 0 to 100% [5] This
sensor exhibits a good accuracy, with hysteresis less than 2% r h It takes only
about 1 s to reach 90% of the steady-state value (90% response time)

70 I ’ I I I ‘1

-----
1 kHz
r ----
I.0knz
- - 100 kHz
---1Mnz
1. -
01 ’ 1 I
2oMHz I
0 12 2 33.5 54 5 75.5 97
Relative humldlty /%
Fig 7 Frequency dependence of capacitance-humldlty characterlstlcs of ‘Humwape’
sensor
 387

The porosity of the humidity-sensitive polymer 1s important to obtam

quick responses The stress-induced fracture techmque proposed by
Delaplerre et al [ 161 appears to be useful m this respect A porous chromium
electrode has been evaporated under condltlons such that the humldlty-
sensitive film 1s tensile stressed The stresses cause a lot of cracks m the
polymer, resulting in an mcrease m the penetration rate of water vapour by
several orders of magnitude
Recent improvements m polylmlde processmg for integrated circuit
(IC) and mterlay dlelectnc apphcatlons enables a humidity sensor to be
fabncated on an Sl chip [17,18] This techmque realizes a small, low cost
humidity sensor, and, probably most Important, It becomes possible to
integrate the humidity sensor with other sensors or signal-handling clrcultry
on the same chip [18] Polylmldes have been successfully apphed on Sl chips
as humldlty-sensitive dlelectrlcs urlth high mechanical strength, high temper-
ature capability, and high resistance to chermcal attack The sensitivity and
response depend upon the sensor geometry, including the electrodes
According to Glenn et al [18], bulk capacitance IS more suitable for
humidity sensors than surface capacitance, with respect to reproduclblhty
of sensor fabrication, lmearlty to relative humidity and hysteresis As the
porous upper electrode, a perforated electrode can be obtamed by means of
a photohthographlc technique
It 1s worth notmg that a mlcrochlp humidity sensor based on a fleld-
effect transistor (FET) was recently developed by HiJikigawa et al [ 19, 201
The FET hunudlty sensor, integrated with a temperature-sensing diode, was
fabricated as shown m Fig 8 with standard IC processing techmques The
host FET device was an n-channel MISFET mth a meandering-gate structure
Crosslmked cellulose acetate one rmcron thick is stacked as a humldlty-
sensltlve membrane between the lower gate electrode and the upper gate
electrode (porous gold electrode, 100 - 200 A thick) An equivalent clrcult
of this sensor 1s shown m Fig 9 A d c voltage V, and a small a c voltage u.
are applied to the upper gate electrode The upper and lower gates are
electncally connected mth a sufflclently large fixed resistance RB It 1s
show-n that, under adequate condltlons, the output voltage, Vout, 1s related
ulth the capacitance of the membrane, C,, as follows
V out= ~oR,g,l(l + G/G) (1)

where RL IS the load reslstor connected with the dram electrode, g, 1s the
transconductance of the FET, and C, the capacitance of the gate insulator
With C, dependent on ambient relative hunudlty and the other constants
surtably chosen, V,, can be correlated almost hnearly with relative
humidity, as shown m Fig 10 This sensor has been ssud to show a good
accuracy (hystereas less than 3% r h ) with a response time less than 30 s
Long-term stability and a good durability agamst high relative humidity (90 -
95% r h ) and dew drops have also been claimed These excellent capablhtles
seem to be due to the adoption of the a c operating method It 1s remarked
that the same pnnclple may be applied to other gas sensors, provided
388

I \
IGFET (p-S1)
I \ /
I
"
FET HUMIDITY SENSOR TEKPERATURE SENSOR

Fig 8 Schematlc cross-section of FET humldlty sensor

"DD
Ti
a
230
:,
3
200

J_ 170
“0 T 0 20 40 60 80 100
Relative humldlty /%
Fig 9 Equivalent cxcult of FET humidity sensor
Fig 10 Output V,,, us relative humidity of FET humidity sensor at 25 “C (5'0= 2 5 V,
vo=300mV,f=lOkHz)

appropriate gas-sensltlve membranes are found Further advances m this

technique are eagerly awaited

4. Porous ceranuc hunudlty sensor

From the vlewpomts of mechamcal strength, temperature capablhty

and resistance to chemical attack, ceramic materials appear to be the most
suitable candidates for chemical sensors A number of lnvesixgatlons have so
far been carned out for humldlty sensors utlhzmg porous ceramic elements
[ 21 - 293 These sensors utlhze either the Impedance [21 - 271 or the
capacitance [28,29] of the elements for humidity detection The impedance
type consists of lonlc 121 - 241 and electronic types [25 - 271
 389

4 1 Ionic-type humldlty sensor

4 1 1 Relatlonshrps between mxrostructure and water adsorption
It 1s well known that water molecules undergo chemlsorptlon and
physlsorptlon on the surface of oxldes The chemlsorptlon, which 1s the
stronger process, causes dlssoclatlon of water molecules to form surface
hydroxyls Physlsorptlon then takes place on top of this The water
molecules m the first physlsorbed layer are doubly hydrogen bonded to
two surface hydroxyls and cannot move or rotate freely The water
molecules m the second and succeeding layers, however, are singly hydrogen
bonded to sublayers and are more free to rotate [30], which 1s important
for Grotthuss-type transport of protons It 1s borne m mmd that the
structure of physlsorbed water changes from an ordered ice-lrke one for a
monolayer to a hquld-hke one for multllayers as physlsorptlon proceeds
If there are pores, capillary condensation of water vapour takes place
m addltlon to the above adsorption When the pores are cyhndlncal with one
end closed, condensation occurs m all pores with radu up to rx given by
the followmg Kelvin equation (Route I)
2YM
rx = (2)
pRT In P,/P
where rx stands for the Kelvin radius, y, p and M for the surface tension,
density and molecular weight of water, respectively, and P and P, for water
vapour pressures m the surroundmg environment and at saturation,
respectively When the cyhndrlcal pores are open at both ends (open pores),
hysteresis 1s observed m the capillary condensation isotherms In the
adsorption process, water is condensed In pores with radn up to rK/2, while
the desorptlon is determined by rx (Route II) [ 311
Actual porous ceramic elements have pores of both types, each of these
pores IS by no means a cylinder with a urnform radius and 1s better descrrbed
as a senal chain of short constituent pores (umt pores) nnth different radn
These pores mterconnect each other m the porous elements and make up a
threecllmenslonal network In this situation, capillary condensation depends
not only on the pores radms but also on whether the adJacent umt pores are
filled with condensed water or not, condensation via Route I or II takes
place correspondmgly A slmulatlon study has suggested that condensation
via Route I 1s more dominant and that more than half of the pores with radn
rx are filled with condensed water [32]

4 1 2 Relatlonshlp between humldlty sensltlvtty and microstructure

Many ceramic matenals have been investigated for lomc-type humrdlty
sensors [21 - 24, 331 The importance of mlcrostructure as well as mtnnslc
impedance of the sensor element have been pointed out [23,24, 331, but
the actual relatlonshlps between humidity sensltlve charactenstlcs and the
microstructure were not studied until recently The fact that most of the
ceramic humidity sensors developed have large porosltles rangmg from 25
to 50% [23,24,34 - 371 suggests the importance of capillary condensation,
390

especially at high humidity (r h 40%) [ 381 Simulation analysis of

impedance-humidity charactenstlcs was carned out to demonstrate this
[ 39,401 A model sensor element was assumed to have strmght cyhndlncal
pores runnmg parallel between two plate electrodes Other assumptions were
that capillary condensation takes place via Route I for all pores, and that
only capillary-condensed water contnbutes to a change m impedance
Supposing the pore size dlstrlbutlons (a), (b) and (c) shown m Fig 11, the
Impedance-humldlty charactenstlcs of the model sensor were simulated
respectively as shown m Frg 12 [39] In this slmulatlon, the mtrmslc
Impedance of the sensor was taken to be 10’ SLand the conductlvlty of con-
densed water to be 8 20 X 10e7 S cm- 1 With the pore size dlstnbutlon (a),
the impedance changed only m a narrow humldlty range below 10% r h ,
because all the pores were filled unth condensed water vapour m this range
The diffuse pore size dlstrlbutlon (b) mcreased the sensltlvlty only shghtly at
higher relative humldltles The more comphcated dlstrlbutlon (c) gave lnse to
a favourable impedance-humldlty charactenstlc These results mdlcate that
the pore size dlstnbutlon or microstructure IS declslvely important for the
sensing charactenstlcs

Pore size, d/;i Pore size, d/;f

Ca) (b) 2
.
10 -c!
a06
2
li
P5

-0123456

0 5
0 01 02 0396 98 0 20 40 60 80 100
pore sxze, d/ii Relative bumLdity /%
Cc)
Fig 11 Pore size dastnbutlons of model sensor

Fig 12 Impedance (Z)-humldlty charactenstlcs of model sensor with pore size

dlstnbutlon shown In Fig 11 (a) to (c), respectively

The slmulatlon analysis was extended to two actual porous ceramic

elements, MgA1204 and MgFezOQ [40] The elements were observed to have
the pore size dlstnbutrons shown m Fig 13 From these mlcrostructural
data, the impedance-humldlty charactelnstlcs were simulated as the broken
lines m Frg 14 The simulated characterlstlcs are seen to represent well the
mam features of the actually observed ones shown by the sohd hnes It 1s
 391

(a) 0

II,
0 08
5

I
s
0 04 6-

0
0 10 2 0 3 0 0 20 40 60 80 100
(b) Pore size, d/A x102 Relative humldlty /%

Fig 13 Pore size dlstrlbutlons of the elements after bolhng treatment (a) MgAl204, (b)
MgFe204
Fig 14 Impedance (Z)-humidity characterlstlcs of MgAl204 and MgFez04 elements at
20 “C after boIlmg treatment Open and closed circles, MgAl204, open and closed squares,
MgFe20g Sohd lmes, observed, dotted hnes, calculated

concluded that the sensmg charactenstlc of this type of sensor IS mamly

determined by capillary condensation of water m the pores

4 1 3 Examples of ronw-type humldlty sensors

Table 3 shows various examples of lonlc-type ceramic humidity sensors
Most elements have large porosltles and mde pore size dlstnbutlons A
humidity sensor using MgCr,O,-no,, developed by Nltta et al, was put into
practical use m microwave ovens m 1978 [ 41, 481 Later, the element was
improved to also have sensltlvlty to reducing gases such as alcohols and
smokes Figure 15 shows a schematic view of the multlfunctlonal sensor,
which measures relative humidity at temperatures up to 150 “C and responds
to reducmg gases at 400 - 500 “C The sensing element IS a tiny, porous,
rectangular wafer of a MgCr,O,-?‘lO, spine1 sohd solution The RuOz
electrodes attached are very porous to assure gas permeablhty The resistance
of the element decreases exponentially as relative humidity increases over
the whole hunudlty range, as shown m Fig 16, with a response time less
than 10 s The conduction mechanism at low relative humidity has been sard
to be the mlgratlon of the protons dlssoclated from the surface hydroxyl
groups, while at higher relative humidity Grotthuss-type proton conduction
takes place through capillary-condensed water As has been also found m
other ceranuc sensors of this type, the base resWance of the element
TABLE 3
Character&cs of lomc-type ceramic humldlty sensors

Matenal Shape of element Pore size ParWe 51ze Porosrty Impedance (ii!) Temp Refs
dlstnbution (av ) {%) (“C)
lO%rh 90%rb
(pm) &m)
Rectangular wafer - 03 33 10 M 10 k 20 23
4X5x025mm 41
Rectangular wafer 04 - 10 07 45 13M” 40 k 20 36
5Ox26x15mm
C~cuhr wafer 0 001 - 10 0 05 47 25M 25k 20 42
100X05mm
Circular wafer 01 - 04 02 41 1M f4k 25 37
100XlOmm
Thick film (20pm) 1 -10 - 5M 3k 25 44
=lOxlOmm 45
ZnCr~04_LiZnV04 C2rcularwafer 01 - 04 03 12 300 k’ 4k 25 46
80xO2mm 47

*At 30% r h
 393

electrode

0 20 40 60 80 100
Relative humldlty /%
Fig 15 Configuratlon of multlfunctlonal ceramw sensor

Fig 16 Resistance-humldlty characterlstlcs of multlfunctlonal ceramic sensor at several

temperatures

increases gradually during operation This dnft seems to be related wrth the
increase of surface hydroxyl groups, which impede Grotthuss-type proton
conduction To overcome this unfavourable phenomenon, the element IS
heat cleaned at temperatures above 360 “C before each operation by means
of one of the RuOz electrodes
A porous m02-V205 sensor developed by Katayama et al IS also based
on lomc conduction [36] A small amount of V,O, additive (1 mol %) IS
effective to control mtnnslc electmcal conductlvlty, pore size dlstnbutlon
and average particle size of the elements A farly good humidity sensltlvlty
with a response time less than 10 s has been reported
Recent mvestlgatlons have shown that the mtroductlon of small
amounts of alkah ions has a favourable effect on cerarmc humidity sensors
The alkah Ions added act as dominant charge carriers instead of protons and
thus often endow the sensors with higher humidity sensltlrnty as well as base
resistance stability For example, although a pure MgFe,O, element 1s very
poor m sensltlvlty, the addition of 2 mol % of K*, Ll+ or Na+ can greatly
improve the sensltlvlty over the whole range of relative humidity, as shown
m Fig 17 [39] This improvement results m part from the change of mlcro-
structure of the element
The effects of alkali ions have been emphasized m the thick film S102-
based sensor by Uchlkawa et al [43 - 451 The film prepared by the heat
treatment of a mixture of slhcone polymer and slhca gel was humidity
sensltlve, but had an mtrmslc resistance larger than 3 G&X The addition of
sodium ions to the system lowered the mtrmslc resistance urlthout lmpau-mg
the humidity sensltlvlty A ceramic sensor using ZnCr,OQ-LlZnV04,
developed by Yokomlzo et al [ 46,47,49], consisted of ZnCrzOg grams 2 -
3 pm m size, which were covered with a thm glazed film of LlZnV04 In this
case, hydrated Ll+ ions seem to contribute to charge transport and
394

3
t I I I I I
0 20 40 60 80 100
Relative hunudlty /%
Fig 17 Resistance-humldlty charactemtlcs of WON04 mth alkali ion addltwes at 25 “C

sensltlvlty The last two ceranuc sensors hardly show a dnft m resistance and
can be operated without heat cleanmg, unhke the proton conduction-type
sensors The addition of alkali ions thus appears to be quite effective m
several respects, but the technique may cause a new problem about how to
keep the alkah ions stable on the surface m such a case as dew condensation
All the above ceramic humidity sensors are operated below 150 “C A
humidity sensor using ankmonlc acid (a proton conductor) has been
mvestlgated for operation between 100 and 200 “C [50]

4 2 Electronw-type humrdlty sensors

It 1s known that water molecules act as an electron donatmg gas on
semlconductlve oxides In fact, semiconductor gas sensors, which are used
wdely to detect reducing gases, are known to suffer from mterfenng effects
of water vapour under certam condltlons [ 511
In response to demands for operation at elevated temperatures, seml-
conductor humidity sensors using Srl_XLaXSnO~ 1271 and ZrOzMgO [26]
have been proposed In these sensors, the loganthm of the electronic
resistance of the element IS linearly correlated with the logarithm of the
water vapour concentration [27] The microstructure of the elements, such
as surface area and average particle size, has a less pronounced effect on
sensmg characterlstlcs than m the lonlc-type humldlty sensors Just
mentioned [ 521 The electronic-type sensors can be operated with d c volt-
age Interferences of reducing gases (except ethanol) are negligibly small for
Srl _,La,Sn03 The interference of ethanol can be suppressed by coating
the elements unth Pt/A1203 catalyst [ 531

4 3 Capacztwe humldlty sensor

Alumma films prepared by reactive ion plating, anodlc oxldatlon and
vapour deposltlon are known to be sensltlve to humrdlty m both capacltlve
and resistive measurements [28, 29, 54, 551 Here we deal with a capacltlve
 395

humidity sensor compnsmg a porous, thm alumma film sandwiched by two

parallel plate electrodes, which can be prepared with conventional IC
processmg techniques The capacitance of the alumina film increases with an
increase m relative hunudlty due to the large relative permlttlvlty of the
adsorbed water Control of microstructure of the film 1s agam important for
sensing characterlstlcs, and the film preparation condltlons should be
carefully chosen m the reactive ion platmg [56] and the anodlc oxldatlon
[57] To obtam quick responses, the upper electrode should be as thm and
porous as possible
Figure 18 shows a cross-section of a 1 mm2 humidity-sensltrve MOS
capacitor [ 57 ] A porous, thm alumma layer was prepared by anodizing the
1 pm thick alummmm evaporated on slhcon dioxide The porous upper
electrode of gold was defined by a photohthographlc technique The
humldlty-sensltlve MOS capacitor can be mcorporated m the gate of a
MOSFET, as described previously The humiditydependent capacitance can
be detected from a varlatlon of the dram current This sort of approach 1s
Important, because progress m integration techmques will enable us to
reahze soph&lcated or mtelhgent sensors m the future

bonding pad (Au)

Porous electrode (Au) I

I porous Al203
s109

p-s1

Al

Fig 18 SchematIc cross-sectlon of humldlty-sensltlve MOS capacitor

References

F W Dunmore, An electrometer and its apphcatlon to radio meteorography, J

Res Nat Bur Std , 20 (1938) 723 - 744
F W Dunmore, An improved electric hygrometer, J Res Nat Bur St, 23 (1939)
701- 714
K Shlba, Measurement of detailed dlstrlbutlon of humldlty, Asahi-kugaku, 16 (1956)
79 - 83
Y Yamada, Lithium chlonde humidity sensor, Denshr-gyutsu, 21 (9) (1979) 26 - 30
Nakaasa Instrument Co Ltd , Catalogue, C911-84001-15K-2D (1984) p 78
K Otsuka, S Kmokl and T Usul, Organic polymer humidity sensor, Denshz-zowyo,
(Sept 1980) 68 - 73
M Hqlkigawa, S Mlyoshl, T SuQ;lhara and A Jmda, A thm-film resistance humldlty
sensor, Sensors and Actuators, 4 (1983) 307 - 315
T Suphara and S Mlyoshl, Humldlty sensor usmg polyelectrolyte, Sensa-ggutsu. 3
(7) (1983) 41 - 44
P H Huang, Electncal and thermodynamic characterlzatlon of water vaporjpoly-
menc film system for humldlty sensing, Digest of Technrcal Papers, 3rd Int Conf on
396

Solrd-State Sensors and Actuators {Transducers’ 85). Phlladelphra, PA, US A , June

11 - 14,1985, pp 206 - 208
10 S Tsuchltanl, T Sugawara, H Kmjo and S Ohara, Humldlty sensor usmg iomc
copolymer, Digest of Techmcal Papers, 3rd Int Conf on Sohd-State Sensors and
Actuators (Transducers’ 85), Phzladelphza, PA, US A , June 11 - 14, 1985, pp 210 -
212
11 Y Sakal, Y Sadaoka and K Ikeuchl, Humidity sensors composed of graft
copolymers, Digest of Technacal Papers, 3rd Int Conf on Salad-State Sensors and
Actuators (Transducers’ 85), Phzladelphla, PA, US A , 1985, pp 213 - 216
12 T Ishlda, T Kobayashl, K Kuwahara and H Hatanaka, Dew sensor composed of
resin and carbon, Nat Tech Rep, 24 (1978) 436 - 444
13 E Salasmaa and P Kostamo, New thm fdm humidity sensor, Vazsala News, NO 66
(1975)
14 Valsala KK, Catalogue, Ref No A 9371
15 S Sakural, Humlcape humidity sensor, Sensa-grlutsu, 2 (6) (1982) 175 - 177
16 G Delaplerre, H Grange, B Chambaz and L Destannes, Polymer-based capacitive
humldlty sensor, charactenstlcs and experimental results, Sensors and Actuators, 4
(1983) 97 - 104
17 D D Denton, S D Sentuna, E S Anohck and D Schelder, Fundamental issues in
the design of polymeric capacltlve moisture sensors, Dtgest of Technical Papers, 3rd
Int Conf on SohdState Sensors and Actuators (Transducers’ 85), Phthdelphta, PA,
US A, June 11 - 14,1985, pp 202 - 205
18 M C Glenn and J A Schuetz, An IC compatable polymer humidity sensor, Dzgest
of Technrcal Papers, 3rd Int Conf on Solzd-State Sensors and Actuators
(Transducers’ 85), Phzladelphza. PA, US A , June 11 - 14,1985, pp 217 - 220
19 M Hqikigawa, H Furubayashl, S Mlyoshl and Y Inaml, A micro humldlty sensor
based on a field-effect transmtor, F’roc 4th Sensor Symp, Tsukuba, Japan, May 31 -
June 1. 1984. pp 135 - 140
20 M Hipkigawa, T Suglhara, J Tanaka and M Watanabe, Microchip FET humldlty
sensor with a long-term stability, Dagest of Technrcal Papers, 3rd Znt Conf on Solzd-
State Sensors and Actuators (Transducers’ 851, Phzladelphza, PA, US A, June I1 -
14, pp 221 - 224
21 M Matsuura and M Matsuoka, Humidity dependence of reslstlmty of potassium-
modified ferric oxide ceramics, Funtal-oyobr-funmatsuyaktn. 23 (1976) 242 - 249
22 R T Johnson, Jr and R M Blefeld, Ionic conductlvlty of LlgAlO4 and LlSGeOd in
moist environment, potential humldlty sensors, Mater Res Bull, 14 (1979) 537 -
542
23 T Nltta, Z Terade and S Hayakawa, Humldltysensltlve electrlcal conduction of
MgCr20cmO2 porous ceramics, J Am Ceram Sac , 63 (1980) 295 - 300
24 Y Shlmlzu, H Aral and T Selyama, Ceramic humidity sensors I Microstructure and
humldlty sensitive characteristics of spmel type oxides, Denkl Kagaku, 50 (1982)
831- a34
25 H Taguchl, Y Takahashl and C Matsumoto, The effect of water adsorption on
(Lal-,Sr,)MnOs (0 1 x 0 5), Yogyo-kyokaz-shz, 88 (1980) 566 - 570
26 T Nltta, F Fukushlma and Y Matsuo, Water vapor gas sensor using ZrOz-MgO
ceramic body, Proc Int Meet on Chemzcal Sensors, Kodansha, 1983, pp 387 - 392
27 H Aral, S Ezakl, Y Shlmlzu, 0 Shlppo and T Selyama, Semlconductlve humldlty
sensor of perovsklte-type oxides, Proc Int Meet on Chemzcal Sensors, Kodansha,
1983, pp 393 - 398
28 K Suzuki, K Koyama, T Inuzuka and Y Nabeta, Alumina thin film humldlty sensor
controlbng of humidity characterlstlcs and aging, Proc 3rd Sensor Symp , Tsukuba,
Japan, June 9 - 10, 1983, pp 251 - 256
29 V K Khanna and R K Nahar, Effect of moisture on the dielectric properties of
porous alumina films, Sensors and Actuators, 5 (1984) 187 - 198
30 E McCafferty and A C Zettlemoyer, Adsorption of water vapor on (Y-Fe203, DZSC.
Famday Sot, (1971) 230 - 255
 397

31 J H de Bore, The shapes of caplllarles, In The Structure and Properties of Porous

Materials,, Butterworth, London, 1958, pp 68 - 94
32 Y Morloka and J Kobayashl, Sorption hysteresis and network structure of pores In
porous substances Part I -[Link] of capillary condensation m adsorption
process, Nappon Kaguku Kazsha (1979) 157 - 163
33 Y Sadaoka and Y Sakal, Humldlty sensltlvlty of smtered porous alumma and
alumina-bona, Denkl Kagaku, 51 (1983) 873 - 878
34 T Nltta, Ceramic humldlty sensor, Ind Eng Chem Res Develop, 20 (1981) 669 -
674
35 T Nltta, J Terada and F Fukushlma, MultIfunctIonal ceramic sensors humldlty-gas
sensor and temperature-humldlty sensor, IEEE Trans Electron Devzces, ED-29 (1982)
95 - 101
36 K Katayama and T Aklba, Rut11 humldlty sensor, Proc Int Meet on Chemwal
Sensors, Kodansha, 1983, pp 433 - 438
37 T Suzuki and N Matsul, Properties of humidity sensltlve oxldes with alkah addltlve,
Proc Int Meet on Chemwal Sensors, Kodansha, 1983, pp 381 - 386
38 B M Kulwlckl, Ceramic sensors and transducers, J Phys Chem Solads, 45 (1984)
1015 - 1031
39 T Seiyama, N Yamazoe and H Aral, Ceramic humldlty sensors, Sensors and
Actuators, 4 (1983) 85 - 96
40 Y Shlmlzu, H Aral and T Selyama, Theoretical studies on the Impedance-humidity
charactenstlcs of ceramic humldlty sensors, Sensors and Actuators, 7 (1985) 11 - 22
41 T Nltta, Z Terada and T Kanazawa, Ceramic humidity sensor ‘Humlceram’, Nat
Tech Rep, 24 (1978) 422 - 435
42 Y Shlmlzu, H Ichmose, H Arm and T Selyama, Ceramic humldlty sensors - micro-
structure and slmulatlon of humldlty sensltlve characterlstlcs, Nappon Kagaku Kaasha
(1985) 1270 - 1277
43 F Uchlkawa, K Shlmamoto, T Hasegawa and T Yoshlda, Conduction mechamsms
and time dependence of sensmg characterlstlcs on SIOZ humldlty sensltlve films,
Hyomen Kagaku (1984) 233 - 240
44 F Uchlkawa, K Mlyao, K Shlmamoto and K Nakamshl, Surface OH concentration
and electrlcal resistance of hymldlty-sensltlve slhcon composite films, Ceram Bull ,
63 (1984) 1043 - 1046
45 F Uchlkawa and K Shlmamoto, mrne varlablhty of surface lonlc conduction on
humldltysensltlve SlOz fdms Am Ceram Sot Bull, 64 (1985) 1137 - 1141
46 Y Yokomlzo, S Uno, M Harata and H Hirakl, Microstructure and humldlty-sensitrve
propertles of ZnCrzO4-LkZnV04 ceramic sensors, Sensors and Actuators, 4 (1983)
599 - 606
47 S Uno, M Harata, H Hlrakl, K Sakuma and Y Yokomlzo, ZnCrzOcLiZnV04
ceramic humidity sensor, Proc Int Meet on Chemrcal sensors, Kodansha, 1983, pp
375-380
48 T Nltta and Z Terada, Ceramic humldlty sensltlve reslstor device, Nat Techn Rep,
22 (1976) 885 - 894
49 N Ichmose, Electronic ceramics for sensors, Am Ceram Sot Bull, 64 (1985) 1581 -
1585
50 N Mlura, I Yashlma and N Yamazoe, Humldlty-sensmg characteristics of antimomc
acid proton conductor element at medmm temperature, Nippon Kagaku Karshr
(1985) 1581 - 1585
51 G N Advam and L Narus, Effects of humldlty on hydrogen sulphlde detection by
SnOz solid state gas sensors, Sensors and Actuators, 2 (1981/82) 201 - 206
52 Y Shlmlzu, M Shlmabukuro, H Aral and T Selyama, Enhancement of humid&y
sensltlvlty for perovsklte-type oxides havmg semlconductlvlty, Chem Lett , (1985)
917 - 920
53 Y Shlmlzu, 0 Shlppo, H Aral and T Selyama, Influence of reducmg gases on the
sensitlvlty of the semlconductlve humid:ty sensor, Denkr Kagaku, 52 (1984)
849 - 850
54 Y Sadaoka and Y Sakal, A humldlty sensor using porous thm film of anodized
alumina, Proc Int Meet on Chemzcal Sensors, Kodansha, 1983, pp 416 - 421
55 M Takeuchq Y Mmamlya, F Kaneko and H Nagasaki, ElectrIcal propertles of
anodized alummlum gas sensors, Proc Int Meet on Chemzcal Sensors, Kodansha,
1983, pp 422 - 427
56 Y Nabeta, Charactenstics and rehablhty of A1203 thm film humldlty sensor, Proc
Int Meet on Chemzcal Sensors, Kodansha, 1983, pp 410 - 415
57 G J Rogers, L C Westcott, R A Dames, H 0 Ah, G H Swallow and E Read,
Humldlty sensitive MOS structures, Proc Znt Meet on Chemzcal Sensors, Kodansha,
1983, pp 428 - 432

Blographles

Noboru Yamaxoe recewed the B Eng Degree In Appbed Chemistry m

1963 and the Dr Eng degree m 1969 from Kyushu Umverslty He Jomed
the Faculty of Engmeenng m Kyushu Umverslty In 1968 and moved to the
Graduate School of Engmeenng Sciences m Kyushu Unlverslty m 1979 He
has worked on mixed oxide catalysts, semiconductor gas sensors, solid
electrolyte sensors and humldlty sensors

Yasuhwo Shrmzzu received the B Eng degree in Apphed Chemistry m

1980 from Kyushu Unlverslty He Jolned the Graduate School of
Engmeenng Science m Kyushu University m 1981 and moved to the Faculty
of Engmeenng m Nagasaki Unlverslty m 1986 He has worked on the
development of humidity sensors and oxygen sensors