JOURNAL OF APPLIED PHYSICS VOLUME 92, NUMBER 12 15 DECEMBER 2002

Quantitative evaluation of chemisorption processes on semiconductors

A. Rothschilda) and Y. Komem
Faculty of Materials Engineering, Technion–Israel Institute of Technology, Haifa 32000, Israel
N. Ashkenasyb)
Department of Electrical Engineering–Physical Electronics, Tel Aviv University, Tel Aviv 69978, Israel
共Received 31 May 2002; accepted 12 September 2002兲
This article presents a method for numerical computation of the degree of coverage of
chemisorbates and the resultant surface band bending as a function of the ambient gas pressure,
temperature, and semiconductor doping level. This method enables quantitative evaluation of the
effect of chemisorption on the electronic properties of semiconductor surfaces, such as the work
function and surface conductivity, which is of great importance for many applications such as solid-
state chemical sensors and electro-optical devices. The method is applied for simulating the
chemisorption behavior of oxygen on n-type CdS, a process that has been investigated extensively
due to its impact on the photoconductive properties of CdS photodetectors. The simulation
demonstrates that the chemisorption of adions saturates when the Fermi level becomes aligned with
the chemisorption-induced surface states, limiting their coverage to a small fraction of a monolayer.
The degree of coverage of chemisorbed adions is proportional to the square root of the doping level,
while neutral adsorbates are independent of the doping level. It is shown that the chemisorption of
neutral adsorbates behaves according to the well-known Langmuir model, regardless of the
existence of charged species on the surface, while charged adions do not obey Langmuir’s isotherm.
In addition, it is found that in depletive chemisorption processes the resultant surface band bending
increases by 2.3kT 共where k is the Boltzmann constant and T is the temperature兲 when the gas
pressure increases by one order of magnitude or when the doping level increases by two orders of
magnitude. © 2002 American Institute of Physics. 关DOI: 10.1063/1.1519946兴

I. INTRODUCTION well known,1– 6 the correlation with the environmental con-

Chemical adsorption 共chemisorption兲 on semiconductors
induces surface states and surface dipoles, modifying the sur-
face density of states and the position of the Fermi level at
the surface.1– 6 Consequently, it affects the electronic proper-
ties of semiconductor surfaces, such as the work function and
surface conductivity. This effect is used for monitoring the
ambient gas atmosphere by means of solid-state gas sensors
from semiconducting metal oxides such as SnO2 and TiO2 . 7
In addition, chemisorption of ambient gases, primarily oxy-
gen, is known to have a strong effect on the photoconductiv-
ity of ZnO and CdS,8 and on the photoluminescence intensity
of GaAs and InP.9 It has also been reported that chemisorp-
tion affects the performance of semiconductor-based
catalysts,3,4 solar cells,10,11 and varistors.12 Moreover, in re-
cent years there has been a growing interest in surface modi-
fication and organic functionalization of conventional semi-
conductors 共mainly Si and GaAs兲 by attachment of organic
molecules to their surfaces, in order to produce semiconduc-
tors with tailored surface properties and synthesize novel hy-
brid organic/semiconductor materials.13–15 Thus, it is of great
interest to know the effect of the ambient gas atmosphere on
the surface properties of semiconductors.
Although the relationship between the surface band
bending and the chemisorption-induced surface charge is
a兲
Author to whom correspondence should be addressed; electronic mail:
mtavner@tx.technion.ac.il
b兲
Currently at: The Scripps Research Institute, La Jolla, CA 92037.
ditions 共i.e., the ambient gas pressure and temperature兲 is
known only qualitatively. The lack of quantitative under-
standing of this phenomenon stems from the fact that elec-
tronic charge transfer between the semiconductor and chemi-
sorbed species modifies the electronic structure at the surface
and in the adjacent space charge region, which in return af-
fects the chemisorption process in a nonlinear manner. In
depletive chemisorption a potential barrier is built up at the
surface, which inhibits further charge transfer to the
surface.1– 6 Consequently, the heat of adsorption and the
semiconductor’s adsorptivity decrease with increasing cover-
age of chemisorbed adions.1,16 Most adsorption isotherms,
such as the well-known Langmuir isotherm,17 do not account
for this variation of the adsorption heat as a function of cov-
erage, and therefore they are inadequate to describe chemi-
sorption on semiconductors.
Unlike these simplistic approaches, Wolkenstein’s theory
of chemisorption takes into account these electronic interac-
tions and their effect on the adsorptivity of semiconductors.4
Wolkenstein’s isotherm, ⌰⫽ ␤ P/(1⫹ ␤ P), gives the func-
tional relationship between the degree of coverage of chemi-
sorbates 共⌰兲 and the ambient gas pressure P. However, it
cannot be solved analytically since the adsorption coefficient
␤ is a nonlinear function of ⌰.4 Therefore, numerical com-
putation methods are necessary in order to solve it. Another
complication arises from the fact that chemisorbed adions
contribute to the semiconductor’s surface charge, which must
be balanced by a space charge in the adjacent region in order

0021-8979/2002/92(12)/7090/8/$19.00 7090 © 2002 American Institute of Physics

J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy 7091

to maintain electroneutrality. Therefore, in order to obtain a

self-consistent solution of the problem, Wolkenstein’s iso-
therm and the charge balance equation must be solved simul-
taneously. The solution of these transcendental equations en-
counters mathematical difficulties, and, to the best of our
knowledge, a general solution of the problem has never been
presented in the literature, limiting the discussion of chemi-
sorption on semiconductors to be qualitative in nature and
lacking a quantitative understanding of this phenomenon.
In this work we present a method for quantitative evalu-
ation of the degree of coverage of chemisorbates and the
resultant surface band bending as a function of the ambient
gas pressure, temperature, and semiconductor doping level.
The method is based on numerical computation of Wolken-
stein’s isotherm and the charge balance equation. The pro-
posed method enables quantitative correlation between the
electronic properties of semiconductor surfaces and the en-
vironmental conditions. Obviously, this is of great impor-
tance for device modeling of semiconductor gas sensors, but
it is also of much interest for other semiconductor applica-
tions such as photocatalysts, photodetectors, solar cells, and
varistors, whose performance is affected by chemisorption.
The article is organized as follows. The computational
method is described in Sec. II. Section III presents numerical
simulations of the chemisorption behavior of oxygen on
n-type CdS as a function of the oxygen pressure, tempera-
ture, and doping level. In Sec. IV we make a comparison
with experimental data from the literature, and discuss the
validity of the proposed method and its generality. The con-
clusions are summarized in Sec. V.
FIG. 1. Energy-band diagram for acceptor-like chemisorption on an n-type
semiconductor: 共a兲 At the beginning of chemisorption; 共b兲 at thermal equi-
0 ⫺
librium. A ⬁ , A chem and A chem designate a free atom in the gas phase, a
II. NUMERICAL COMPUTATION OF WOLKENSTEIN’S
neutral adatom, and a negatively charged adion, respectively.
ISOTHERM

The functional relationship between the degree of cover-

age of chemisorbed species 共⌰兲 and the gas pressure P was
derived by Wolkenstein4
⌰⬅N/N * ⫽ ␤ P/ 共 1⫹ ␤ P 兲 ,
where ␤ is the adsorption coefficient
ture. The term ␣ ⫽ ␬ s 0 /(2 ␲ M kT) 1/2, where ␬ is the sticking
probability, s 0 is effective area of a chemisorbed adparticle,
and M is the molecular mass of the gas.
共1a兲
It is worth noting that the adsorption coefficient ␤ de-
pends on the terms (E Cs ⫺E F ) and (E F ⫺E As ). These terms
depend on the surface band bending eV s 共as depicted in Fig.

冋
␤ ⫽ ␤ 0 1⫹
1 ␯⫺
gA ␯0
exp ⫺ 冉
E Cs ⫺E F
kT
冊册
⫺1
1兲, which is a function of the surface charge density that
depends on the degree of coverage ⌰. 4 Thus, Wolkenstein’s
isotherm is an implicit function and it cannot be solved in

冋
⫻ 1⫹
1
gA
exp 冉
E F ⫺E As
kT
冊册 共1b兲
and ␤ 0 ⫽ ␣ ( ␯ 0 ) ⫺1 exp(q0/kT) is the adsorption coefficient
from the well-known Langmuir isotherm.17 N and N * are the
number of chemisorbates and the number of chemisorption
sites per unit area, respectively, q 0 is the adsorption heat of
the neutral form of chemisorption, E F is the Fermi level, E Cs
is the conduction band edge at the surface, and E As is the
energy level of the chemisorption-induced surface states,18 as
depicted in Fig. 1. g A is the degeneracy factor of the
chemisorption-induced states, ␯ 0 and ␯ ⫺ are the oscillation
frequencies of the neutral and charged chemisorbed species,
respectively, k is Boltzmann’s constant, and T is the tempera-
closed form. Moreover, in order to solve Wolkenstein’s iso-
therm self-consistently, the effect of chemisorption on the
electronic structure at the surface and in the adjacent space
charge region must be taken into account. Since chemisorbed
adions contribute to the semiconductor’s surface charge, Eq.
共1兲 should be solved simultaneously with the electroneutral-
ity condition. This can be done by reducing the problem to a
single variable and solving it numerically.
Thus, the proposed method for the numerical computa-
tion of Wolkenstein’s isotherm involves calculating the sur-
face charge density Q s and the space charge density Q sc as a
function of the surface potential V s , and evaluating the
charge balance equation Q s (V s )⫹Q sc(V s )⫽0 in order to ob-
tain the equilibrium surface potential V s0 . Assuming that
7092 J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy

TABLE I. Parameters used for the simulations of oxygen chemisorption on n-type CdS.

Physical property Symbol Value

Band gap energy Eg 2.42 eVa

Energy level of the chemisorption-induced states (E Cs ⫺E sA ) 0.8 eVb
Degeneracy factor for the chemisorption-induced states gA 2c
Effective mass for electrons in the conduction band m e* 0.21m 0 a,d
Effective mass for holes in the valence band m*h 0.8m 0 a,d
Dielectric constant of the semiconductor substrate ⑀ 5.4a
Density of chemisorption sites N* 1015 cm⫺2
Effective area of a chemisorbed adparticle s0 10⫺15 cm2
Sticking probability ␬ 1
Adsorption heat for the neutral chemisorbed state q0 0.1 eV
Oscillation frequency of the neutral chemisorbed state ␯0 1013 s⫺1
Oscillation frequency of the charged chemisorbed state ␯⫺ 1013 s⫺1
Molecular mass of O2 M 32 amu
a
S. M. Sze, Physics of Semiconductor Devices, 2nd ed. 共Wiley, New York, 1981兲.
b
Reference 19.
c
For univalent adparticles the degeneracy of the empty states is 1 whereas that of the occupied states is 2 共since
there are two electrons at the same energy level兲, therefore g A ⫽2.
d
m 0 is the electron mass in free space.

chemisorption is the only source for surface charging and
that each chemisorbed adion captures one electron, the sur-
face charge density is
Q s ⫽⫺eN ⫺ ⫽⫺e f A⫺ ⌰N * ,
where N ⫺ is the number of chemisorbed adions per unit area
(N ⫺ ⫽ f A⫺ N), and f A⫺ is the Fermi–Dirac distribution func-
tion. In order to calculate Q s as a function of V s , both f A⫺
and ␤ 关Eq. 共1b兲兴 are written as explicit functions of V s
v s ⬅eV s /kT, u b ⬅(E F ⫺E bi )/kT⫽ln(nb /ni), E bi is the intrin-
sic Fermi level in the bulk, and n i is the intrinsic charge
density.
共2兲 After calculating both Q s (V s ) 兩 T ⬘ , P ⬘ and Q sc(V s ) 兩 T ⬘ as a
function of V s , the electroneutrality condition Q s (V s ) 兩 T ⬘ , P ⬘
⫹Q sc(V s ) 兩 T ⬘ ⫽0 is applied in order to obtain the equilibrium
surface potential V s0 兩 T ⬘ , P ⬘ at T ⬘ and P ⬘ . Substituting the re-
sultant V s0 兩 T ⬘ , P ⬘ into Eq. 共4兲 gives ␤ 兩 T ⬘ , P ⬘ , which yields
⌰ 兩 T ⬘ , P ⬘ using Eq. 共1a兲. In addition, substituting V s0 兩 T ⬘ , P ⬘ into

f A⫺ ⫽ 冋 1⫹g A exp ⫺冉 E Cs ⫺E As
kT
冊 冉
exp
E Cb ⫺E F
kT
冊 Eq. 共3兲 yields f A⫺ 兩 T ⬘ , P ⬘ , which enables calculating separately
the degrees of coverage of charged and neutral chemisor-
bates, ⌰ ⫺ 兩 T ⬘ , P ⬘ and ⌰ 0 兩 T ⬘ , P ⬘ , respectively. ⌰ ⫺ ⬅N ⫺ /N *

冉 冊册 ⫽ f A⫺ ⌰ and ⌰ 0 ⬅N 0 /N * ⫽(1⫺ f A⫺ )⌰, where N ⫺ and N 0 are

⫺1
eV s
⫻exp ⫺ 共3兲 the number of charged and neutral chemisorbates per unit
kT
area, respectively. In order to obtain the entire isotherm,
and these calculations should be repeated for various gas pres-

冋
␤ ⫽ ␤ 0 1⫹
1 ␯⫺
gA ␯ 0
exp ⫺
E Cb ⫺E F
kT
冉
exp
eV s
kT
冊 冉 冊册
⫺1 sures. The chemisorption behavior at different temperatures
and doping levels can be evaluated by repeating these calcu-
lations while changing each parameter separately.

冋
⫻ 1⫹
1
gA
exp冉E Cs ⫺E As
kT
exp ⫺ 冊 冉 kT
冊 冉 冊册
E Cb ⫺E F
exp
eV s
kT
, III. SIMULATIONS OF THE CHEMISORPTION
BEHAVIOR OF OXYGEN ON N-TYPE CdS
共4兲 The computational method described above was applied
where E Cbis the conduction band edge in the bulk 共see Fig. for simulating the chemisorption behavior of oxygen on
1兲. For a given temperature T ⬘ and gas pressure P ⬘ , the n-type CdS. This process was thoroughly investigated in the
surface charge density Q s can be calculated as a function of past mainly due to its impact on the photoconductive prop-
V s , using Eqs. 共1兲–共4兲. erties of CdS photodetectors 共see Refs. 8 and 19 for reviews兲.
At this stage the space charge density Q sc should also be It was found that CdS has no intrinsic surface states 共of non-
calculated as a function of V s . For a semi-infinite homoge- adsorptive origin兲, and that chemisorption of oxygen intro-
neous semiconductor under thermal equilibrium, the relation- duces surface states at ⬃0.8 eV below the conduction band
ship between Q sc and V s is readily obtained from Gauss’s edge of CdS.8,19 Thus, the O2 /CdS system is well suited for
theorem and Poisson’s equations5,6 testing our method. In addition, the simulation’s results can

冋 册
cosh共 u b ⫹ v s 兲
Q sc⫽ 冑2 共 n b ⫹p b 兲 eL D ⫺ v s tanh u b ⫺1
cosh u b
where n b and p b are the bulk concentrations of free electrons
and holes, respectively, L D is the extrinsic Debye length,5,6
be compared with experimental data that have been reported
1/2
, for this system.8,19 The calculations were carried out for three
different doping levels 共N D ⫽1014, 1016, and 1018 cm⫺3 ) at
共5兲 T⫽300 K, and for three different temperatures (T⫽300,
400, and 500 K兲 at N D ⫽1016 cm⫺3 . The other parameters
used for these simulations are given in Table I.
J. Appl. Phys., Vol. 92, No. 12, 15 December 2002
FIG. 2. Calculations of 兩 Q s 兩 and Q sc as a function of e 兩 V s 兩 for chemisorp-
tion of oxygen on n-type CdS with N D ⫽1016 cm⫺3 at T⫽300 K. 兩 Q s 兩 is
calculated for various oxygen pressures as indicated in the figure.
Figure 2 demonstrates the computation of the space
charge density Q sc(V s ) 兩 T ⬘ 共at T ⬘ ⫽300 K兲 and the surface
charge density Q s (V s ) 兩 T ⬘ , P ⬘ 共at T ⬘ ⫽300 K and various pres-
sures P ⬘ ) as a function of the surface band bending e 兩 V s 兩 .
The crossover points between these curves give the pertinent
solutions for the equilibrium surface potential V s0 兩 T ⬘ , P ⬘ at the
given temperature T ⬘ and oxygen pressure P ⬘ , since at these
points the electroneutrality condition is satisfied. As can be
seen in Fig. 2, there is a single solution for each oxygen
pressure, and with increasing pressures the crossover points
move rightwards and V s0 兩 T ⬘ , P ⬘ increases in magnitude.
The equilibrium surface potential barrier (e 兩 V s0 兩 ) was
calculated as a function of the oxygen pressure 共P兲 for vari-
ous temperatures 共T兲 and doping levels (N D ) by means of a
dedicated computer program.20 The results are shown in Fig.
3, where Fig. 3共a兲 gives the dependence on the doping level
共at T⫽300 K兲 and Fig. 3共b兲 gives the temperature depen-
dence 共with N D ⫽1016 cm⫺3 ). One can see that e 兩 V s0 兩 is pro-
portional to log10 P for a wide range of pressures. A similar
logarithmic relationship between the surface barrier and the
ambient oxygen pressure has been observed in CdS
and ZnO,19,21 but it has not been explained adequately
to date. Figure 3 also demonstrates that the slope
d(e 兩 V s0 兩 )/d(log10 P) is independent of the doping level 关see
Fig. 3共a兲兴, but it does depend on the temperature 关see Fig.
3共b兲兴. In order to clarify the relationship between the surface
band bending and the oxygen pressure, Fig. 4 depicts
d(e 兩 V s0 兩 )/d(log10 P) as a function of T, and it is found that
d(e 兩 V s0 兩 )/d(log10 P)⫽2.3kT. It is interesting to note that
e 兩 V s0 兩 increases by the same value (2.3kT) also when the
doping level (N D ) increases by two orders of magnitude, as
shown in Fig. 3共a兲. These relationships can be derived from
Wolkenstein’s isotherm under certain approximations 共see
the Appendix兲.
Substituting the results obtained for e 兩 V s0 兩 as a function
of P back into Eq. 共4兲 and using Eq. 共1a兲 enables us to
calculate the degree of coverage of oxygen chemisorbates
共⌰兲 as a function of the oxygen pressure. Moreover, the de-
gree of coverage of charged adions ⌰ ⫺ ⬅N ⫺ /N * ⫽ f A⫺ ⌰ and
neutral adsorbates ⌰ 0 ⬅N 0 /N * ⫽(1⫺ f A⫺ )⌰ can be calcu-
Rothschild, Komem, and Ashkenasy 7093
FIG. 3. The equilibrium surface band bending e 兩 V s0 兩 as a function of the
oxygen pressure P: 共a兲 For three different doping levels 共as indicated in the
figure兲 at T⫽300 K; 共b兲 for three different temperatures 共as indicated in the
figure兲 with N D ⫽1016 cm⫺3 . The insets show e 兩 V s0 兩 as a function of P on a
rectilinear plot.
lated separately, using Eq. 共3兲. The results are shown in Fig.
5, where Fig. 5共a兲 shows the dependence on the doping level
共at T⫽300 K兲 and Fig. 5共b兲 shows the temperature depen-
dence 共with N D ⫽1016 cm⫺3 ). At low oxygen pressures
共P⬍10⫺3 atm兲 ⌰⬇⌰ ⫺ Ⰷ⌰ 0 , i.e., nearly all oxygen chemi-
sorbates are in the charged state. At higher pressures ⌰ ⫺
approaches saturation while ⌰ 0 continues to grow monotoni-
cally. Eventually, at some point ⌰ 0 becomes larger than ⌰ ⫺
共see insets in Fig. 5兲. This complies with the expected behav-
ior for such a depletive chemisorption process. At low gas
pressures the surface is relatively clean 共i.e., nearly adsorbate
free兲 and the band bending e 兩 V s 兩 is small. In this case, the
adsorption heat of the charged form of chemisorption, q ⫺
⫽q 0 ⫹(E Cb ⫺E As ), is greater than that of the neutral form, q 0
共see Fig. 1兲.4 Thus, the charged state is energetically more
favorable than the neutral state and most species chemisorb
as charged adions. As the gas pressure increases, more and
more adions chemisorb and the surface charge density in-
creases in magnitude. Consequently, e 兩 V s 兩 increases 共see Fig.
3兲 and q ⫺ decreases, i.e., the charged form of chemisorption
becomes less favorable with respect to the neutral form,
7094 J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy

FIG. 4. The slope d(e 兩 V s0 兩 )/d(log10 P) as a function of kT, as obtained from

Fig. 3共b兲.

whose heat of adsorption (q 0 ) is independent of the degree

of coverage. As a result, at some point the neutral form of
chemisorption becomes predominant.
Figure 5 shows that ⌰ ⫺ approaches saturation when P
increases and that the degree of coverage of charged adions
does not exceed a small fraction of a monolayer 共e.g., ⌰ ⫺
⭐2⫻10⫺3 for doping levels as high as 1018 cm⫺3 ). The
saturation of the charged form of chemisorption results from
the pinning of the Fermi level at the semiconductor surface
when it becomes aligned with the energy level of the
chemisorption-induced surface states, i.e., when (E F ⫺E As )
⫽0.1– 4 This restricts the degree of coverage of chemisorbed
adions to a limit, ⌰ ⫺ 兩 sat , that correlates to the surface band
bending at saturation, e 兩 V s 兩 sat⫽(E Cs ⫺E As )⫺(E Cb ⫺E F ). Our
FIG. 5. The degree of coverage of chemisorbed oxygen species as a func-
numerical calculations indicate that this limit
tion of the oxygen pressure P: 共a兲 For three different doping levels 共as
is only a small fraction of a monolayer; ⌰ ⫺ 兩 sat⬇2⫻10⫺5 , indicated in the figure兲 at T⫽300 K; 共b兲 for three different temperatures 共as
2⫻10⫺4 , and 2⫻10⫺3 for N D ⫽1014, 1016, and 1018 cm⫺3 indicated in the figure兲 with N D ⫽1016 cm⫺3 . Solid line⫽⌰; dashed line⫽
共at T⫽300 K兲, respectively 关see Fig. 5共a兲兴. These values cor- ⌰ ⫺ ; dashed-dot line⫽⌰ 0 . The insets show a magnified picture for the high-
respond to surface charge densities of 2⫻1010, 2⫻1011, and pressure range. Note that in 共a兲 the ⌰ 0 curves for the three doping levels
overlap each other. ML⫽monolayer.
2⫻1012 electrons/cm2 , respectively.
The degree of coverage of adions depends on the doping
level at all pressures, as shown in Fig. 5共a兲. This arises from 5共b兲兴 and ⌰ Lang , the coverage obtained from Langmuir’s iso-
the fact that chemisorption of adions involves free electrons therm under the same conditions, i.e., from Eq. 共1兲 with ␤
and therefore the higher the doping level more free electrons ⫽ ␤ 0 . It shows that the ⌰ 0 and ⌰ Lang curves overlap with
are available for this process and consequently ⌰ ⫺ increases. each other, indicating that both isotherms yield the same re-
Figure 5共a兲 shows that ⌰ ⫺ is proportional to the square root sults for the coverage of neutral adsorbates. Indeed, the ef-
of the doping level, i.e., ⌰ ⫺ ⬀N D 1/2
. This result can be de- fective adsorption coefficient for the neutral form of chemi-
rived from the expression for the space charge density for sorption, which may be written as (1⫺ f A⫺ ) ␤ , is
depletion layers 共the depletion approximation兲,2,6 Q sc approximately the same as the adsorption coefficient ␤ 0 in
⬇(2 ⑀⑀ 0 N D e 兩 V s 兩 ) 1/2, since Q sc⫽⫺Q s ⫽e⌰ ⫺ N * and e 兩 V s 兩 Langmuir’s isotherm 关see also Eq. 共A1兲 in the Appendix兴.
is only a weak function of the doping level 关see Fig. 3共a兲兴. Thus, it is found that Wolkenstein’s isotherm for the neutral
The term ⑀ is the dielectric constant of the semiconductor form of chemisorption actually reduces to the well-known
and ⑀ 0 is the permittivity in free space. As opposed to the Langmuir isotherm.
charged form of chemisorption, the neutral form involves no
electronic charge transfer between the semiconductor and the
IV. DISCUSSION
adsorbates, and therefore ⌰ 0 is independent of the doping
level, as shown in Fig. 5共a兲. Thus, it could be expected that The simulation of the chemisorption behavior of oxygen
Langmuir’s model should give a satisfying description of the on n-type CdS clearly demonstrates the characteristic fea-
chemisorption behavior of the neutral adsorbates, regardless tures of depletive chemisorption on semiconductors, and the
of the existence of charged species on the surface. In order to results are in agreement with the general behavior of such a
test this hypothesis, Fig. 6 compares between ⌰ 0 关from Fig. process, as discussed above. While the main features are al-
J. Appl. Phys., Vol. 92, No. 12, 15 December 2002
FIG. 6. Comparison between ⌰ 0 关from Fig. 5共b兲兴 and ⌰ Lang 关calculated
from Eq. 共1兲 with ␤ ⫽ ␤ 0 ] as a function of the oxygen pressure, for n-type
CdS (N D ⫽1016 cm⫺3 ) at T⫽300, 400, and 500 K 共as indicated in the
figure兲. Solid line⫽⌰ 0 ; open circles⫽⌰ Lang . ML⫽monolayer.
ready known qualitatively, this work elaborates the under-
standing of chemisorption on semiconductors much further
by providing a method for quantitative evaluation of these
processes. Thus, it enables one to calculate the
chemisorption-induced modifications in the electronic prop-
erties of semiconductor surfaces as a function of the environ-
mental conditions.
It was found that in depletive chemisorption the surface
band bending e 兩 V s 兩 increases by 2.3kT when the gas pressure
increases by one order of magnitude or when the doping
level increases by two orders of magnitude, as shown in
Figs. 3 and 4. These logarithmic relationships can explain
quantitatively experimental results that were unexplained un-
til now. For instance, in Ref. 19 it was reported that the
electrical conductivity activation energy in n-type CdS
共N D ⬇1016 cm⫺3 ) increased by approximately 0.07 eV per
decade increase of the ambient oxygen pressure. A similar
logarithmic relationship between the surface band bending
and the ambient oxygen pressure was reported also in Ref.
21. These experimental observations are in excellent agree-
ment with our numerical calculations, as depicted in Fig. 7.
共We note that the experimental data in Ref. 19 refer to the
activation energy E act⫽(E Cb ⫺E F )⫹e 兩 V s 兩 , where (E Cb ⫺E F )
⬇0.21 eV and e 兩 V s 兩 reflects the oxygen chemisorption equi-
librium at T⬇400 K.兲 The excellent fitting between the ex-
perimental data and the simulation’s results corroborates the
validity of the proposed computational method and demon-
strates its strength in quantitative evaluation of the electronic
properties of semiconductor surfaces as a function of the
environmental conditions.
The proposed computational method is based on Wolk-
enstein’s theory of chemisorption on semiconductors,4 com-
bined with the electroneutrality condition and the appropriate
expressions for the space charge density and surface charge
density. Therefore, it can be applied to any semiconductor/
gas system that satisfies the postulations of Wolkenstein’s
model: 共i兲 coexistence of both charged and neutral states of
chemisorbed species on the surface 共corresponding to the
Rothschild, Komem, and Ashkenasy 7095
FIG. 7. Comparison between the calculated curve of e 兩 V s0 兩 ⫹0.21 eV 共for
n-type CdS with N D ⫽1016 cm⫺3 at T⫽400 K兲 and the experimental data
from Ref. 19. Dashed line ⫽ calculated curve; full squares ⫽ experimental
data.
‘‘strong’’ and ‘‘weak’’ forms of chemisorption in Wolken-
stein’s theory兲; 共ii兲 noninteracting adsorbates; and 共iii兲 intrin-
sic surface states are either absent or insensitive to
chemisorption.4 The coexistence of both charged and neutral
forms of chemisorption was confirmed experimentally and it
is widely accepted nowadays.3,22 It is in accord with many
experimental observations that the adsorbate uptake proceeds
beyond the saturation of the chemisorption-induced surface
charge.2,22 This is attributed to chemisorption of neutral ad-
sorbates that do not affect the surface charge, as discussed
above 共see also Fig. 5兲. According to the second postulation,
noninteracting adsorbates are considered, and therefore the
model is valid only for submonolayer coverages. However,
in the case of depletive chemisorption the degree of coverage
of charged adions is limited to a small fraction of a mono-
layer, and therefore this restriction is satisfied. The third pos-
tulation is adequately discussed in Refs. 3 and 22. It may
apply for ionic semiconductors such as GaAs, InP, and CdTe,
which are free of intrinsic surface states and exhibit no band
bending in the adsorbate-free 共ultraclean兲 state.2,6 This is true
also for defect-free surfaces of oxide semiconductors of the
rutile structure, such as SnO2 and TiO2 . 23,24 Therefore, the
proposed computational method may be adequate for such
materials, especially under ultrahigh vacuum or controlled
environmental conditions. Indeed, simulations of the chemi-
sorption behavior of oxygen on TiO2 共not shown here for the
sake of brevity兲 agree with the experimental observations for
this system.25 However, if the semiconductor has a high den-
sity of band gap states of nonadsorptive origin, such as in-
trinsic or defect-induced surface states, the Fermi level could
be pinned at these states. In such cases the semiconductor
can interact with fewer charged adsorbates and its electronic
properties are less sensitive to chemisorption than semicon-
ductors with no such states.26 Such a scenario when there
is more than one mechanism controlling the pinning of
the Fermi level at semiconductor surfaces is discussed in
Ref. 22.
7096 J. Appl. Phys., Vol. 92, No. 12, 15 December 2002
Although the original form of Wolkenstein’s isotherm,
Eq. 共1兲, was derived exclusively for nondissociative
chemisorption,4 the model can be elaborated to include also
dissociative chemisorption by modifying the adsorption iso-
therm to account for the respective changes in the condensa-
tion coefficient.6,27 For instance, the appropriate adsorption
isotherm for chemisorption of a gas that dissociates into two
species on the surface 共e.g., H2 ) would have the functional
form ⌰⫽( ␤ P) 1/2/(1⫹( ␤ P) 1/2) instead of Eq. 共1兲.4 Thus,
the computational method can be generalized also for disso-
ciative chemisorption by making the proper modifications in
the adsorption isotherm.
While in the present work we discuss mainly depletive
chemisorption, the proposed method can be applied also for
accumulative or inversion chemisorption processes because
Eq. 共5兲 is valid for the entire range of V s . 5,6 However, it
should be noted that Eq. 共5兲 applies only for semi-infinite
homogenous semiconductors.5,6 Practically, this means that
the computational method presented in this work applies as it
is only for films that are thicker than the depletion layer
width, which is typically ⬃1000 Å.6 In order to generalize it
for thinner films, Eq. 共5兲 should be replaced with the correct
expression for Q sc as a function of V s , taking into account
the finite film thickness and the charge density on its other
side. This expression can be obtained by solving Poisson’s
equation and Gauss’s theorem with the proper boundary
conditions.28,29
V. SUMMARY AND CONCLUSIONS
A numerical computation method for quantitative evalu-
ation of the chemisorption behavior of gases on semiconduc-
tors was presented. The method enables calculating the cov-
erage of neutral and charged chemisorbates and the resultant
surface band bending as a function of the environmental con-
ditions 共the gas pressure and temperature兲 and the electronic
properties of the semiconductor substrate 共the doping level兲
and semiconductor/adsorbate system 共the energy level of the
chemisorption-induced surface states兲.
The method was applied for simulating the chemisorp-
tion behavior of oxygen on n-type CdS as a function of the
oxygen pressure, temperature, and doping level. This simu-
lation satisfies the expected chemisorption behavior, demon-
strating the saturation of the charged form of chemisorption
when the Fermi level becomes aligned with the
chemisorption-induced surface states. As a result of the pin-
ning of the Fermi level at these states, the degree of coverage
of chemisorbed adions does not exceed more than a small
fraction of a monolayer.
It was found that in depletive chemisorption the degree
of coverage of chemisorbed adions is proportional to the
square root of the doping level, and that the resultant surface
band bending increases by 2.3kT when the gas pressure in-
creases by one order of magnitude or when the doping level
increases by two orders of magnitude. These relationships
provide simple quantitative correlations between the elec-
tronic properties of semiconductor surfaces and the environ-
mental conditions. This is important for understanding the
Rothschild, Komem, and Ashkenasy
impact of the environmental conditions on semiconductor
devices, e.g., for gas sensor applications.
ACKNOWLEDGMENTS
This work was partially supported by the Technion V. P.
R. Fund–I. Goldberg Fund for Electronics Research, and by
the Fund for the Promotion of Research at the Technion. A.
R. would like to thank the generous financial support of the
Israel Ministry of Science 共Eshkol Fellowship兲 and the Israel
Council for Higher Education.
APPENDIX: DERIVING THE APPROXIMATED
RELATIONSHIPS BETWEEN THE SURFACE BAND
BENDING AND THE AMBIENT GAS PRESSURE
AND SEMICONDUCTOR DOPING LEVEL
FROM WOLKENSTEIN’S ISOTHERM
In all the numerical calculations in this work ␤ PⰆ1 was
obtained. Therefore, Wolkenstein’s isotherm 关Eq. 共1a兲兴 may
be written approximately as ⌰⬇ ␤ P. Assuming that the fre-
quencies ␯ 0 and ␯ ⫺ are of the same order of magnitude,4 the
term in the first square brackets on the right-hand side of Eq.
共1b兲 is approximately equal to 1. Thus, the adsorption coef-
ficient ␤ may be approximated as
冋 冉 冊册
1 E F ⫺E As
␤ ⬇ ␤ 0 1⫹ exp ⫽ ␤ 0 共 1⫺ f A⫺ 兲 ⫺1 . 共A1兲
gA kT
Therefore, ⌰⬇ ␤ 0 (1⫺ f A⫺ ) ⫺1 P, and the number of chemi-
sorbed adions per unit area is
N ⫺ ⫽N * f A⫺ ⌰⬇N * ␤ 0 关共 f A⫺ 兲 ⫺1 ⫺1 兴 ⫺1 P. 共A2兲
Substituting Eq. 共3兲 into Eq. 共A2兲 and using the relationship
(E Cb ⫺E F )/kT⫽ln(NC /ND), where N C is the effective density
of states in the conduction band, yields
N ⫺ ⬇C 0 exp共 ⫺e 兩 V s 兩 /kT 兲 P, 共A3兲
where C 0 ⫽N * ␤ 0 g A⫺1 (N D /N C )exp关(ECs⫺EAs)/kT兴. From the
charge neutrality condition and the depletion approximation6
we obtain eN ⫺ ⫽ 兩 Q s 兩 ⫽Q sc⬇(2 ⑀⑀ 0 N D e 兩 V s 兩 ) 1/2. Substituting
this relation into Eq. 共A3兲 yields
共 e 兩 V s 兩 兲 1/2exp共 e 兩 V s 兩 /kT 兲 ⬇C 1 N D
1/2
P, 共A4兲
where C 1 ⫽eN * ␤ 0 (2 ⑀⑀ 0 ) ⫺1/2g A⫺1 N C⫺1 exp关(ECs⫺EAs)/kT兴.
Taking the common logarithm from both sides of Eq. 共A4兲
gives
1.15kT log10共 e 兩 V s 兩 兲 ⫹ 共 e 兩 V s 兩 兲
⬇2.3kT 关 log10 C 1 ⫹log10 N D
1/2
⫹log10 P 兴 . 共A5兲
Taking the constant-temperature derivatives from both sides
of Eq. 共A5兲 yields
0.5共 e 兩 V s 兩 /kT 兲 ⫺1 d 共 e 兩 V s 兩 兲 ⫹d 共 e 兩 V s 兩 兲
⬇2.3kT 关 d 共 log10 N D
1/2
兲 ⫹d 共 log10 P 兲兴 . 共A6兲
Finally, for e 兩 V s 兩 ⰇkT Eq. 共A6兲 may be approximated as
d 共 e 兩 V s 兩 兲 ⬇2.3kT 关 d 共 log10 N D
1/2
兲 ⫹d 共 log10 P 兲兴 . 共A7兲
Equation 共A7兲 indicates that the surface band bending e 兩 V s 兩
should increase by 2.3kT when the doping level increases by
J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy 7097

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