IEEE TRANSACTIONS ON ELECTRON DEVICES. VOL. 39. NO. 4.
APRIL 1992
Modeling H+-Sensitive FET's with SPICE
Massimo Grattarola, Giuseppe Massobrio, and Sergio Martinoia
Abstract-A generalized physical model including two kinds
of binding sites is presented for H+-sensitive ISFET devices.
The model results in a set of equations which is introduced into
a modified version of the electronic circuit simulation program
SPICE. In this way, the effects induced on the device perfor-
mances by varying several physico-chemical parameters are
analyzed.
The slope of V,,, versus pH curves is predicted for SiOz-,
A1203-, and Si3N4-gate ISFET's. The program outputs are
checked by comparing them with experimental data obtained
with an Al,O,-gate ISFET. The model is then used to predict
the behavior of a hypothetical, partially pH-insensitive
(REFET) structure. Finally, the model is utilized to fit the slow
response of the Al,O,-gate ISFET to a pH step.
I. INTRODUCTION
I N RECENT YEARS, much work has been done to
characterize ion-sensitive devices (ISFET's) based on
MOS technology. H+-sensitive ISFET's are perhaps the
most accurately modeled devices as far as their physical
and chemical behavior is concerned. The response of
H+-sensitive devices in aqueous solutions is commonly
explained by using the so-called site-binding model [ 11.
According to this model, the presence of ion-specific
binding sites at the surface of the insulator exposed to the
electrolyte is responsible for the ion-dependent charge
distribution on the insulating layer. A detailed compari-
son between this and other models for Si02 is given in
[2]. Most of the models refer to this insulator as the gate
insulator, although it has very limited practical use be-
cause of its well-known unstable response [3]. Among the
most suitable insulators, A1203 is considered in several
papers [4], [5], while, to the best of our knowledge, the
more complex insulator Si3N, (two kinds of binding sites)
is analyzed only in [6]. In that paper, after briefly sug-
gesting a parametric method for the exact analytical so-
lution of a two-site system, the authors propose an expres-
sion, relating p H to the electrolyte-insulator voltage,
which implies several approximations. This equation,
originally deduced in [4], is quite useful, as it allows a
direct evaluation of the system behavior, but the intro-
duced simplifications make it somewhat inadequate to
fully characterize the device in any arbitrary physico-
Manuscript received November 20. 1990; revised March 4 , 1991. This
work was supported by the National Research Council (CNR) of Italy and
by the Italian Ministry for University and Research (MURST). The review
of this paper was arranged by Associate Editor S. D. Senturia.
The authors are with the Biophysical and Electronic Engineering De-
partment, University of Genova, 16145 Genova. Italy.
IEEE Log Number 9105901.
0018-9383/92$03.00 '81992 IEEE
813
chemical condition. Such a detailed characterization could
be of great importance for a deeper insight into the non-
idealities of these devices [7] and for the design of other
silicon-based potentiometric sensors (cf., for example,
LAPS [SI). In addition, up to now the development of the
physico-chemical theory for the ISFET has not been sup-
ported by any description of the device behavior in a de-
tailed circuit model.
In view of the above considerations, the goals of this
paper are: a) the derivation of a set of equations that al-
lows one to define a relationship between pH and the elec-
trolyte-insulator voltage pc0,for inorganic insulators, in-
cluding those with more than one kind of sites (i.e.,
Si3N4);this approach can be regarded as an extension of
the models developed by other authors [2], [9], and can
be suitably adapted to characterize REFET structures; b)
the use of this set of equations as an input to a modified
version of the electronic circuit simulation program SPICE
[IO], which leads to a complete description of ISFET's
and circuits containing ISFET's. As a result, the behavior
of electronic circuits containing ISFET's based on A1203
and Si3N4gate insulators is analyzed as a function of both
chemical and physical parameters.
EIS STRUCTURE
11. GENERALIZED
In this section, a set of equations is derived to fully
characterize an Electrolyte-Insulator-Semiconductor
(EIS) structure (Fig. 1) with two kinds of binding sites
(i.e., Si3N4).In the next section, these equations will then
be adapted to describe the ISFET behavior.
The meaning of the symbols of the model is given in
Fig. I .
At the surface of the Si,N4 insulator, silanol sites, ter-
tiary amine sites, secondary amine sites, and primary
amine sites are present. We assume that only silanol sites
and basic primary amine sites are present on the surface
after oxidation [6]. Thus the dissociation constants for the
chemical reactions at the insulator interface are [9] (see
Table I)
[SiOH] [H'], O0
K, = = - [H+I,
[SiOHl] 8,
814 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 39, NO. 4, APRIL 1992

B
Fig. 1. n-channel ISFET structure. The voltage drops relevant to the model
are indicated.

TABLE I
INSULATORELECTROCHEMICAL
PARAMETERS
(25°C)

Surface Ionization Constants* Surface Site Density**

Insulator K+ K- KN + N,,,/,, N",, PHX,'

Si02 15.8 63.1 x IO-' - 5.0 x 1014 - 3.0
SiJ4 15.8 63.1 X IO-' 1 X IO-'' 3 . 0 X lOI4 2.0 X IOn4 5.8
A1203 12.6 x IO-' 79.0 x IO-'' - 8.0 x i o t 4 - 8.5

* Moles per liter.

** Numbers per square centimeter.
# pH,,, = p H value at the point of zero charge (U,,)

where [ H f ] , is the concentration of protons on the surface tion between the concentration of protons [ H i ] b in the
of the insulator. solution and at the surface [H'], of the insulator is given
The normalization condition yields by the Boltzmann equation

where peu = (po- p,) is the potential of the electrolyte-

8Nf + 8NO = Nnit
-
NS
(5) insulator interface.
Thus by the Gouy-Chapman-Stem theory, the poten-
80 + 8+ + 8- + O N + + ONO = 1 (6) tial peois expressed as a function of the charge density
in the diffuse layer and of the ion concentration co in the
where NS,,and Nnitare the numbers of silanol sites and solution [4]
primary amine sites per unit area, respectively, and N , is
the total number of available binding sites.
The charge density of the surface sites uo on the insu-
lator is given by
where E, is the permittivity of the solution, and ch is the
(7)
capacitance of the Helmholtz layer.
This well-known result can be expressed in a form more
By combining (1)-(7), we get suitable for SPICE by considering the potentials of the
system in Fig. 1.
[H']: - K + K - By inspection, the following relationships can be writ-
$
00
_ - ten:
qN, - ( [ H i ] : + +
K+[H+], K + K )
(Helmholtz layer)

+
[Hi],
([Hi], +
KN+) %'
To obtain the relationship p H = f(p,,) we are looking ( ~ ~ layer) ~ ~ - ~ h ~ ~
for, the above equation must be completed with the model
for the electrical double layer and with the condition of
charge neutrality of the system in Fig. 1, when the rela-
ad = sinh [
d p g 2kT
- pd) 1. (12)
GRATTAROLA er a l . : MODELING H ‘-SENSITIVE FET‘S WITH SPICE
By combining (1 1) and (12 ) , we obtain
4 conductor surface depletion region charge per unit area.
Equation (13) is identical to (lo), and provides a rela-
tion between the charge density ud in the diffuse layer and
the electrolyte-insulator potential pPothrough the poten-
tial differences at the interfaces in the system in Fig. 1.
In addition, the condition of charge neutrality for the
where umosis the charge density in the semiconductor.
BY taking into count ( 1 1 ) ~(14) can be rewritten as
00 = C h ( ~ o- P~I - umo,
where umo5is given by
om,, = +~2t,k~p,, [(E - 1 + exp (--E))
npo
f -
Ppo
( s‘4 kT
1 + exp I)%(
and rzD0 and pao are the equilibrium concentrations of elec-
trons’and hoies, respectively.
The charge density umos within the semiconductor is
taken positive for ps < 0, and negative for ps > 0.
umoscan also be written as
%“ = Cox(Ps - Po)
where CO,is the insulator capacitance.
The equations obtained by substituting (16) into (17)
and (15) into (8) form, together with (9) and (13), a sys-
tem that describes an EIS structure with two kinds of
binding sites (i.e., Si3N4). The system of equations is
solved for the four variables qd,cpo, ps,and [H ‘1, while
pRis an externally defined parameter. This set of equa-
tions, from now on referred to as the “EIS system,” will
be used to calculate the electrolyte-insulator potential pro.
111. ISFET MODEL
The ISFET behavior can be deduced by combining the
aforesaid EIS structure with the physics of the MOST that
will be summarized in this section.
A . Static Model
The equations describing the behavior of the ISFET can
be derived from the analogous equations of the MOST,
by taking into account the potential differences among the
new elements of the system in Fig. 1. The result is a mod-
ification of the MOST threshold voltage
Qss
vt,(MOST) = Pms + 2 ~ -,
where pmsis the metal-semiconductor work-function dif-
ference, pf is the Fermi potential of the semiconductor
81.5
(p-type for the n-channel MOST considered here), Q,, is
the fixed surface-state charge density per unit area at the
(13) insulator-semiconductor interface, and Qsc is the semi-
By the potentia1 terms Of the ISFET ‘On-
figuration in the definition of the ISFET threshold voltage
v,*,,it can be written
v;*,(ISFET) = E c f + Po> - (P,,,- XPO)
Terms common to (1 8) and (1 9), such as Q,,, Q,, , p,=,
and Cox,retain their conventional definitions according to
the standard MOST theory, while E,,, is the potential of
(15)
the reference electrode, po is the liquid-junction potential
difference between reference solution and the electrolyte,
ppois the potential of electrolyte-insulator interface, xro
is the electrolyte-insulator surface dipole potential, and
I/2
(16)
cpsc / q is the semiconductor work function. The potential
~p,,~, comes out from the solution of the EIS system. For
the n-channel ISFET considered we have utilized an
Ag I AgCl reference electrode.
By comparing (1 8) and (1 9), we can write
(17) where p , / q is the work function of the metal gate (ref-
erence electrode) relative to vacuum. We obtain the
ISFET static model by replacing the MOST threshold
voltage Vth with v,*,in the classic 1-v equations of the
MOST.
B. Large-Signal Model
The ISFET large-signal model is based on the MOST
large-signal model, characterized by two p-n junction de-
pletion-layer capacitances and by the gate-source, gate-
drain, gate-bulk capacitances which in turn are functions
of the insulator capacitance Cox.For the ISFET, the in-
sulator capacitance is sensitive to the ionic activity of the
electrolyte, and consists of two elements connected in se-
ries: the MOST insulator capacitance c,,, and the Helm-
holtz layer capacitance C,,, which has to be considered to
model the large-signal behavior of the ISFET.
IV. ISFET MODELI N SPICE
A . Static Model
The equations describing the MOST static model [ 111
in SPICE have been kept for the ISFET static model, by
replacing the expression for Vt, of the MOST with (20)
+ Q.u
(18) and using the peovalue resulting from the solution of the
cox
EIS system. Thus in addition to the MOST static model
parameters of SPICE, we have introduced ten more pa-
rameters that the user of SPICE can specify in the
~

816 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 39, NO. 4, APRIL 1992

TABLE 11
EXAMPLE
OF .MODEL CARD FOR A n-CHANNEL AI,O,-GATElSFET*

.MODEL isf NMOS LEVEL = 4 TOX = lOON LD = 0.8U XJ = 2U NSUB = 2E15

TPG = 1 U 0 = 520 RD = 85 RS = 85 LAMBDA = 0.02 NSS = 3E10
XQC = 1 IS = 1F CGSO = 40P CGDO = 40P CGBO = 200P
CJ = 200U MJ = 0.5 CJSW = 80N MJSW = 0.33
ztoxn = 90N zepsox = 28.7
zepsil = 0.6 znkap = 0.0 zph = 7.0 ztau = 50
zakap = 12.6N zbkap = 0.79N zscon = 0.1
znox = 8e14 zchl = 20U znnit = 0.0
zerel = 0.205 zchieo = 3M

MlSPD 2 2 1 0 0 isf L = 20U W = 400U AD = lOON AS = lOON PS = 900U PD = 900U.

* The lower case parameters define the ISFET model; the capital parameters are common to MOST and
ISFET model.

.MODEL card to model the static behavior of the ISFET. 150 1

These parameters are: CO(zscon), KN+(znkap),
K + (zakap), K - (zbkap), c h (zchl), NSi,(znox), Nnit(znnit),
pH(zph), E,, (zerel), xeo(zchieo).
Moreover, in order to simulate ISFET’s with more than
one insulator layer (SPICE has only built-in parameters
for a Si02-type insulator), we have introduced two new
parameters for the .MODEL card: the added insulator
thickness toxl(ztoxn) and its dielectric constant
eOx1(zepsox). The round brackets contain the .MODEL
keywords for the new parameters of the ISFET model (see
Table 11).
B. Large-Signal Model
The equations describing the MOST large-signal model
[l 11 in SPICE have been kept for the ISFET large-signal
model, replacing the insulator capacitance CO, of the
MOST with the series of CO,and ch. Thus to characterize
the ISFET large-signal model behavior, the user of SPICE
has to specify the Ch parameter in the .MODEL card.
C. Independent Source
A time-varying pH source has also been implemented
in SPICE in order to simulate the pH behavior in different
experimental situations. The p H source has been intro-
duced as a dummy voltage source. In this way the voltage
source can be introduced without disturbing the electrical
behavior of the circuit and the user can easily plot the p H
waveform, while the running p H value (time dependent)
is used to set the value of [H +Ib in the Boltzmann equa-
tion.
V. RESULTS
A. ISFET Characterization
The input characteristics of “ideal” SO2-, A1203-, and
Si3N4-gate ISFET’s have been simulated by introducing
appropriate values for the equilibrium constants K s (Ta-
ble I) into the EIS system, via the .MODEL card of
SPICE, and by utilizing the other physico-chemical pa-
rameters listed in Table 11.
I :o
-0.5 0.0 0.5 1 .o 1.5
(vgs) gate ~ o ~ t a g e [ v o i t ]
Fig. 2 . AI20,-gate ISFET input characteristics for different pH values and
for a given Vds. Hollow squares indicate experimental data.
Fig. 2 shows the resulting Ids versus Vgs curves (with
source and bulk grounded) for different values of p H and
for a given Vds (i.e., 2 V) in the case of A1203. The sim-
ulated curves are compared with the experimental ones
obtained by performing automatic measurements on
ISFET’s purchased from CSEM (Neuchatel, Switzer-
land).
An estimate of the pH average sensitivity is obtained,
according to (20), by calculating the shifts in V$ (ISFET)
from the SPICE outputs for different p H values. In the
case of A1203, the value obtained is 54 mV/pH. Similar
simulations (not shown) gave, for Si02 and Si3N4, pH
sensitivities of 35 mV /pH and 53 mV /pH, respectively.
All these values correspond quite well to the data reported
in the literature [3]. If the ISFET operating point is
changed (e.g., from Vgs.= 1 V to Vgs = 5 V), a decrease
in pH sensitivity is obtained. In the case of A1203, the pH
sensitivity decreases by about 3 . 0 % , and for SiOz and
Si3N4 the decreases are equal to about 4 . 3 % and 3 . 4 % ,
respectively.
B. Circuit Simulations
In the following, all the SPICE simulations will refer
to circuits where a current-to-voltage conversion is per-
 GRATTAROLA et al.: MODELING H '-SENSITIVE FET'S WITH SPICE 817

-
-

Fig. 3 . Sketch of a feedback circuit for measuring pH sensitivity in ISFET devices.

formed. In this way, realistic experiment conditions can 2 0

be simulated. As an example, we have chosen the mea-

suring circuit proposed in [3]. It is a feedback circuit to .jAl,O,
1 8 -
keep constant the drain current Ids and the drain-source
voltage vds;the output voltage is related directly to vari-
ations in p H via the gate voltage of the ISFET. The circuit
-
~

(a) E 1 I
is sketched in Fig. 3. The reader interested to more details
0
is referred to the original paper [3]. >

I ) Voltage Outputs versus pH: Fig. 4(a) and (b) shows 1 4 - 17

the outputs of the above-mentioned circuit as functions of Ns ixl0
13
Ns 1x10
pH, for A1203 and Si3N4, respectively. The outputs are v, 8x10'4
virtually straight lines when the number of sites given in 1 2 " "

mV /pH for A1203and Si3N4, respectively).

The effect of decreasing the total number of binding
sites ( N , ) is quite evident for the A1203-gate ISFET. A
similar effect is obtained by changing the ratio between
silanol and amine sites for the Si3N4-gate ISFET. In the
latter case, the limiting condition of zero amine sites ob-
viously describes the Si02 behavior.
The reduction in the number of sites induces a depar-
ture from linearity, as expected.
2) REFET Simulations: The EIS system can be easily
adapted in order to simulate surface groups other than sil-
anol or amine. In this way, the behavior of other insula-
tors can be simulated. As an example, a hypothetical
2 4 6 8 10 12
REFET structure with positive groups only has been sim- PH
ulated.
The results obtained with this modified structure are Fig. 4. Effects of changing the number of binding sites on the output volt-
age (Vout). (a) Decresse in the total number of binding sites for an A120,-
shown in Fig. 5. A large region of p H insensitivity is ev- gate ISFET. (b) Decrease in the number of amine sites (with a fixed total

. ident for pH values greater than 5.

3) Nonideal Behavior: pH-sensitive ISFET's are
known to present small drift and hysteresis phenomena.
number of binding sites) in the case of a Si,N,-gate ISFET.

them respond to pH variations with a time delay ~ ( z t a u )

Recently, the problem was addressed in [7], where the
hypothesis that a small number of sites might react slowly
to changes in pH was advanced. This nonideal behavior
can be simulated by our model by splitting the total
amount sites N , into two fractions and by letting one of where E (zepsil) is the fraction of slow-responding sites.
818 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 39, NO. 4, APRIL 1992

1 8 38, , 8.0

1.7

-
c
-
0
1.6

>
0

1.5

1.4 L
2 4 6 8 10 12
‘6.0
-20 0 2G 40 60 80 100
PH Time [arbitrary u n i t ]

Fig. 5. Output voltage of the measuring circuit (Vou,)for a hypothetical (a)

(positive groups only) REFET structure.
37.6 I I

This equation was introduced into the EIS system, and

the resulting modified version was used to simulate the
nonideal response of an ISFET to a single step o f p H (Fig.
6(a)). Fig. 6(b) shows the fitting, obtained with the model,
of the experimental data for an Al2O3-gate ISFET when a
-. one-time constant model
step of p H (7.5 to 7.0) is applied. The values of E and of
the single time constant 7 were chosen arbitrarily, and . Expenmental polnts

should be considered simply as fitting parameters and not T = 25OC

as model predictions. This example was intended to in-
dicate a promising direction in the use of our modified 37 0
version of SPICE. 120 240 360 480 600
Time [ s e c ]

VI. SUMMARY AND CONCLUSIONS

A generalized physical model including two kinds of
binding sites was developed for H +-sensitive ISFET’s,
and introduced into the simulation program SPICE.
The versatility of the modified version of SPICE was
tested by simulating several physico-chemical and circui-
try conditions, and its Outputs were ‘Ompared with ex-
perimental data in the case of A1203-gate ISFET’s.
The obtained results point out the versatility of the pro-
posed model. It is worth noting that the introduction of a
physical model (instead of a circuital macromodel) into
the SPICE program allowed us to simulate, at the phys-
ico-chemical level, a broad range of different situations
such as partial insensitivity to p H (i.e., REFET struc-
tures) and nonideal responses. Moreover, the structure of
the fundamental set of equations (the EIS system) can be
easily modified in order to describe in detail more com-
plex phenomena at the physical level.
Despite the large amount of work done in the past, the
description of the ISFET structure is still fragmentary.
We believe that, thanks to the widespread use of the
SPICE program, our model could be easily used by any
researcher interested in the design and optimization of sil-
icon-based potentiometric sensors and related circuitry.
This opportunity should hopefully result in a greater stan-
dardization of these devices.
Fig. 6. Nonideal response of an ISFET to a single pH step. (a) Simulated
response. (b) Fitting of the slow portion of the experimental response to a
pH step,
ACKNOWLEDGMENT
The authors wish to thank the Centre Suisse D’Electro-
nique et de Microtechnique (CSEM, Neuchatel, Switzer-
land) for providing technical about A1203-gate
ISFET,s.
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[ 111 P. Antognetti and G. Massobrio, Semiconductor Device Modeling with
SPICE. New York: McGraw-Hill. 1988.
Massimo Grattarola received the Laurea degree
in physics from the University of Genova in 1975
In 1977, he joined the Division of Biophysical
and Electronic Engineering of the Electrical Insti-
tute of the University of Genova. which later be-
came the Biophysical and Electronic Engineering
Department (DIBE) At present, he is Associate
Professor of Bioelectronics at the University of
Genova, where he teaches Bioelectronics and Cell
Physiology His research interests include. devel-
opment of cytometric techniques; interfacing neu-
rons with microelectronic devices, modeling of silicon-based blosensors
and their application to monitor the cell microenvironment
819
Giuseppe Massobrio is a Research Associate in
the Department of Biophysical and Electronic En-
gineering (DIBE) of the University of Genova, It-
aly, where he received the degree in Electronic
Engineering in 1976. His extensive background in
semiconductor modeling and simulation includes
teaching and research activities. He is the author
or co-author of several papers on semiconductor
device modeling, and of two books in this field,
one of which is Semiconductor Device Modeling
with SPICE Dublished bv McGraw-Hill. His cur-
rent research interests include the development of models of semiconduc-
tor-based biosensors for biomedical applications.
Sergio Martinoia was born in Sanremo, Italy, in
1964. He received the Laurea degree in electronic
engineering from the University of Genova in
1989. He is currently working toward the Ph.D.
degree in electronic bioengineering at the Univer-
sity of Genova.
Since 1989, he has been working in the Bio-
physical and Electronic Engineering Department
(DIBE) in the areas of solid-state sensor model-
ing, solid-state sensor applications, and develop-
ment of multichannel microelectrodes for signal
recording from networks of cells.