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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 ditions 共i.e., the ambient gas pressure and temperature兲 is
induces surface states and surface dipoles, modifying the sur- known only qualitatively. The lack of quantitative under-
face density of states and the position of the Fermi level at standing of this phenomenon stems from the fact that elec-
the surface.1– 6 Consequently, it affects the electronic proper- tronic charge transfer between the semiconductor and chemi-
ties of semiconductor surfaces, such as the work function and sorbed species modifies the electronic structure at the surface
surface conductivity. This effect is used for monitoring the and in the adjacent space charge region, which in return af-
ambient gas atmosphere by means of solid-state gas sensors fects the chemisorption process in a nonlinear manner. In
from semiconducting metal oxides such as SnO2 and TiO2 . 7 depletive chemisorption a potential barrier is built up at the
In addition, chemisorption of ambient gases, primarily oxy- surface, which inhibits further charge transfer to the
gen, is known to have a strong effect on the photoconductiv- surface.1– 6 Consequently, the heat of adsorption and the
ity of ZnO and CdS,8 and on the photoluminescence intensity semiconductor’s adsorptivity decrease with increasing cover-
of GaAs and InP.9 It has also been reported that chemisorp- age of chemisorbed adions.1,16 Most adsorption isotherms,
tion affects the performance of semiconductor-based such as the well-known Langmuir isotherm,17 do not account
catalysts,3,4 solar cells,10,11 and varistors.12 Moreover, in re- for this variation of the adsorption heat as a function of cov-
cent years there has been a growing interest in surface modi- erage, and therefore they are inadequate to describe chemi-
fication and organic functionalization of conventional semi- sorption on semiconductors.
conductors 共mainly Si and GaAs兲 by attachment of organic Unlike these simplistic approaches, Wolkenstein’s theory
molecules to their surfaces, in order to produce semiconduc- of chemisorption takes into account these electronic interac-
tors with tailored surface properties and synthesize novel hy- tions and their effect on the adsorptivity of semiconductors.4
brid organic/semiconductor materials.13–15 Thus, it is of great Wolkenstein’s isotherm, ⌰⫽ ␤ P/(1⫹ ␤ P), gives the func-
interest to know the effect of the ambient gas atmosphere on tional relationship between the degree of coverage of chemi-
the surface properties of semiconductors. sorbates 共⌰兲 and the ambient gas pressure P. However, it
Although the relationship between the surface band cannot be solved analytically since the adsorption coefficient
bending and the chemisorption-induced surface charge is ␤ is a nonlinear function of ⌰.4 Therefore, numerical com-
putation methods are necessary in order to solve it. Another
a兲 complication arises from the fact that chemisorbed adions
Author to whom correspondence should be addressed; electronic mail:
mtavner@tx.technion.ac.il contribute to the semiconductor’s surface charge, which must
b兲
Currently at: The Scripps Research Institute, La Jolla, CA 92037. 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 ture. The term ␣ ⫽ ␬ s 0 /(2 ␲ M kT) 1/2, where ␬ is the sticking
derived by Wolkenstein4 probability, s 0 is effective area of a chemisorbed adparticle,
and M is the molecular mass of the gas.
⌰⬅N/N * ⫽ ␤ P/ 共 1⫹ ␤ P 兲 , 共1a兲
It is worth noting that the adsorption coefficient ␤ de-
where ␤ is the adsorption coefficient 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.


␤ ⫽ ␤ 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


⫻ 1⫹
1
gA
exp 冉
E F ⫺E As
kT
冊册 共1b兲
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
and ␤ 0 ⫽ ␣ ( ␯ 0 ) ⫺1 exp(q0/kT) is the adsorption coefficient charge region must be taken into account. Since chemisorbed
from the well-known Langmuir isotherm.17 N and N * are the adions contribute to the semiconductor’s surface charge, Eq.
number of chemisorbates and the number of chemisorption 共1兲 should be solved simultaneously with the electroneutral-
sites per unit area, respectively, q 0 is the adsorption heat of ity condition. This can be done by reducing the problem to a
the neutral form of chemisorption, E F is the Fermi level, E Cs single variable and solving it numerically.
is the conduction band edge at the surface, and E As is the Thus, the proposed method for the numerical computa-
energy level of the chemisorption-induced surface states,18 as tion of Wolkenstein’s isotherm involves calculating the sur-
depicted in Fig. 1. g A is the degeneracy factor of the face charge density Q s and the space charge density Q sc as a
chemisorption-induced states, ␯ 0 and ␯ ⫺ are the oscillation function of the surface potential V s , and evaluating the
frequencies of the neutral and charged chemisorbed species, charge balance equation Q s (V s )⫹Q sc(V s )⫽0 in order to ob-
respectively, k is Boltzmann’s constant, and T is the tempera- 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 v s ⬅eV s /kT, u b ⬅(E F ⫺E bi )/kT⫽ln(nb /ni), E bi is the intrin-
that each chemisorbed adion captures one electron, the sur- sic Fermi level in the bulk, and n i is the intrinsic charge
face charge density is density.
Q s ⫽⫺eN ⫺ ⫽⫺e f A⫺ ⌰N * , 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 ⬘
where N ⫺ is the number of chemisorbed adions per unit area ⫹Q sc(V s ) 兩 T ⬘ ⫽0 is applied in order to obtain the equilibrium
(N ⫺ ⫽ f A⫺ N), and f A⫺ is the Fermi–Dirac distribution func- surface potential V s0 兩 T ⬘ , P ⬘ at T ⬘ and P ⬘ . Substituting the re-
tion. In order to calculate Q s as a function of V s , both f A⫺ sultant V s0 兩 T ⬘ , P ⬘ into Eq. 共4兲 gives ␤ 兩 T ⬘ , P ⬘ , which yields
and ␤ 关Eq. 共1b兲兴 are written as explicit functions of V s ⌰ 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-


␤ ⫽ ␤ 0 1⫹
1 ␯⫺
gA ␯ 0
exp ⫺
E Cb ⫺E F
kT

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.


⫻ 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
be compared with experimental data that have been reported
cosh共 u b ⫹ v s 兲 1/2
Q sc⫽ 冑2 共 n b ⫹p b 兲 eL D ⫺ v s tanh u b ⫺1 , for this system.8,19 The calculations were carried out for three
cosh u b 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,
where n b and p b are the bulk concentrations of free electrons 400, and 500 K兲 at N D ⫽1016 cm⫺3 . The other parameters
and holes, respectively, L D is the extrinsic Debye length,5,6 used for these simulations are given in Table I.
J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy 7093

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-
FIG. 3. The equilibrium surface band bending e 兩 V s0 兩 as a function of the
ous temperatures 共T兲 and doping levels (N D ) by means of a oxygen pressure P: 共a兲 For three different doping levels 共as indicated in the
dedicated computer program.20 The results are shown in Fig. figure兲 at T⫽300 K; 共b兲 for three different temperatures 共as indicated in the
3, where Fig. 3共a兲 gives the dependence on the doping level figure兲 with N D ⫽1016 cm⫺3 . The insets show e 兩 V s0 兩 as a function of P on a
共at T⫽300 K兲 and Fig. 3共b兲 gives the temperature depen- rectilinear plot.
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 lated separately, using Eq. 共3兲. The results are shown in Fig.
ambient oxygen pressure has been observed in CdS 5, where Fig. 5共a兲 shows the dependence on the doping level
and ZnO,19,21 but it has not been explained adequately 共at T⫽300 K兲 and Fig. 5共b兲 shows the temperature depen-
to date. Figure 3 also demonstrates that the slope dence 共with N D ⫽1016 cm⫺3 ). At low oxygen pressures
d(e 兩 V s0 兩 )/d(log10 P) is independent of the doping level 关see 共P⬍10⫺3 atm兲 ⌰⬇⌰ ⫺ Ⰷ⌰ 0 , i.e., nearly all oxygen chemi-
Fig. 3共a兲兴, but it does depend on the temperature 关see Fig. sorbates are in the charged state. At higher pressures ⌰ ⫺
3共b兲兴. In order to clarify the relationship between the surface approaches saturation while ⌰ 0 continues to grow monotoni-
band bending and the oxygen pressure, Fig. 4 depicts cally. Eventually, at some point ⌰ 0 becomes larger than ⌰ ⫺
d(e 兩 V s0 兩 )/d(log10 P) as a function of T, and it is found that 共see insets in Fig. 5兲. This complies with the expected behav-
d(e 兩 V s0 兩 )/d(log10 P)⫽2.3kT. It is interesting to note that ior for such a depletive chemisorption process. At low gas
e 兩 V s0 兩 increases by the same value (2.3kT) also when the pressures the surface is relatively clean 共i.e., nearly adsorbate
doping level (N D ) increases by two orders of magnitude, as free兲 and the band bending e 兩 V s 兩 is small. In this case, the
shown in Fig. 3共a兲. These relationships can be derived from adsorption heat of the charged form of chemisorption, q ⫺
Wolkenstein’s isotherm under certain approximations 共see ⫽q 0 ⫹(E Cb ⫺E As ), is greater than that of the neutral form, q 0
the Appendix兲. 共see Fig. 1兲.4 Thus, the charged state is energetically more
Substituting the results obtained for e 兩 V s0 兩 as a function favorable than the neutral state and most species chemisorb
of P back into Eq. 共4兲 and using Eq. 共1a兲 enables us to as charged adions. As the gas pressure increases, more and
calculate the degree of coverage of oxygen chemisorbates more adions chemisorb and the surface charge density in-
共⌰兲 as a function of the oxygen pressure. Moreover, the de- creases in magnitude. Consequently, e 兩 V s 兩 increases 共see Fig.
gree of coverage of charged adions ⌰ ⫺ ⬅N ⫺ /N * ⫽ f A⫺ ⌰ and 3兲 and q ⫺ decreases, i.e., the charged form of chemisorption
neutral adsorbates ⌰ 0 ⬅N 0 /N * ⫽(1⫺ f A⫺ )⌰ can be calcu- 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 Rothschild, Komem, and Ashkenasy 7095

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 FIG. 7. Comparison between the calculated curve of e 兩 V s0 兩 ⫹0.21 eV 共for
CdS (N D ⫽1016 cm⫺3 ) at T⫽300, 400, and 500 K 共as indicated in the n-type CdS with N D ⫽1016 cm⫺3 at T⫽400 K兲 and the experimental data
figure兲. Solid line⫽⌰ 0 ; open circles⫽⌰ Lang . ML⫽monolayer. from Ref. 19. Dashed line ⫽ calculated curve; full squares ⫽ experimental
data.

ready known qualitatively, this work elaborates the under-


standing of chemisorption on semiconductors much further ‘‘strong’’ and ‘‘weak’’ forms of chemisorption in Wolken-
by providing a method for quantitative evaluation of these stein’s theory兲; 共ii兲 noninteracting adsorbates; and 共iii兲 intrin-
processes. Thus, it enables one to calculate the sic surface states are either absent or insensitive to
chemisorption-induced modifications in the electronic prop- chemisorption.4 The coexistence of both charged and neutral
erties of semiconductor surfaces as a function of the environ- forms of chemisorption was confirmed experimentally and it
mental conditions. is widely accepted nowadays.3,22 It is in accord with many
It was found that in depletive chemisorption the surface experimental observations that the adsorbate uptake proceeds
band bending e 兩 V s 兩 increases by 2.3kT when the gas pressure beyond the saturation of the chemisorption-induced surface
increases by one order of magnitude or when the doping charge.2,22 This is attributed to chemisorption of neutral ad-
level increases by two orders of magnitude, as shown in sorbates that do not affect the surface charge, as discussed
Figs. 3 and 4. These logarithmic relationships can explain above 共see also Fig. 5兲. According to the second postulation,
quantitatively experimental results that were unexplained un- noninteracting adsorbates are considered, and therefore the
til now. For instance, in Ref. 19 it was reported that the model is valid only for submonolayer coverages. However,
electrical conductivity activation energy in n-type CdS in the case of depletive chemisorption the degree of coverage
共N D ⬇1016 cm⫺3 ) increased by approximately 0.07 eV per of charged adions is limited to a small fraction of a mono-
decade increase of the ambient oxygen pressure. A similar layer, and therefore this restriction is satisfied. The third pos-
logarithmic relationship between the surface band bending tulation is adequately discussed in Refs. 3 and 22. It may
and the ambient oxygen pressure was reported also in Ref. apply for ionic semiconductors such as GaAs, InP, and CdTe,
21. These experimental observations are in excellent agree- which are free of intrinsic surface states and exhibit no band
ment with our numerical calculations, as depicted in Fig. 7. bending in the adsorbate-free 共ultraclean兲 state.2,6 This is true
共We note that the experimental data in Ref. 19 refer to the also for defect-free surfaces of oxide semiconductors of the
activation energy E act⫽(E Cb ⫺E F )⫹e 兩 V s 兩 , where (E Cb ⫺E F ) rutile structure, such as SnO2 and TiO2 . 23,24 Therefore, the
⬇0.21 eV and e 兩 V s 兩 reflects the oxygen chemisorption equi- proposed computational method may be adequate for such
librium at T⬇400 K.兲 The excellent fitting between the ex- materials, especially under ultrahigh vacuum or controlled
perimental data and the simulation’s results corroborates the environmental conditions. Indeed, simulations of the chemi-
validity of the proposed computational method and demon- sorption behavior of oxygen on TiO2 共not shown here for the
strates its strength in quantitative evaluation of the electronic sake of brevity兲 agree with the experimental observations for
properties of semiconductor surfaces as a function of the this system.25 However, if the semiconductor has a high den-
environmental conditions. sity of band gap states of nonadsorptive origin, such as in-
The proposed computational method is based on Wolk- trinsic or defect-induced surface states, the Fermi level could
enstein’s theory of chemisorption on semiconductors,4 com- be pinned at these states. In such cases the semiconductor
bined with the electroneutrality condition and the appropriate can interact with fewer charged adsorbates and its electronic
expressions for the space charge density and surface charge properties are less sensitive to chemisorption than semicon-
density. Therefore, it can be applied to any semiconductor/ ductors with no such states.26 Such a scenario when there
gas system that satisfies the postulations of Wolkenstein’s is more than one mechanism controlling the pinning of
model: 共i兲 coexistence of both charged and neutral states of the Fermi level at semiconductor surfaces is discussed in
chemisorbed species on the surface 共corresponding to the Ref. 22.
7096 J. Appl. Phys., Vol. 92, No. 12, 15 December 2002 Rothschild, Komem, and Ashkenasy

Although the original form of Wolkenstein’s isotherm, impact of the environmental conditions on semiconductor
Eq. 共1兲, was derived exclusively for nondissociative devices, e.g., for gas sensor applications.
chemisorption,4 the model can be elaborated to include also
dissociative chemisorption by modifying the adsorption iso- ACKNOWLEDGMENTS
therm to account for the respective changes in the condensa-
tion coefficient.6,27 For instance, the appropriate adsorption This work was partially supported by the Technion V. P.
isotherm for chemisorption of a gas that dissociates into two R. Fund–I. Goldberg Fund for Electronics Research, and by
species on the surface 共e.g., H2 ) would have the functional the Fund for the Promotion of Research at the Technion. A.
form ⌰⫽( ␤ P) 1/2/(1⫹( ␤ P) 1/2) instead of Eq. 共1兲.4 Thus, R. would like to thank the generous financial support of the
the computational method can be generalized also for disso- Israel Ministry of Science 共Eshkol Fellowship兲 and the Israel
ciative chemisorption by making the proper modifications in Council for Higher Education.
the adsorption isotherm.
While in the present work we discuss mainly depletive APPENDIX: DERIVING THE APPROXIMATED
chemisorption, the proposed method can be applied also for RELATIONSHIPS BETWEEN THE SURFACE BAND
accumulative or inversion chemisorption processes because BENDING AND THE AMBIENT GAS PRESSURE
AND SEMICONDUCTOR DOPING LEVEL
Eq. 共5兲 is valid for the entire range of V s . 5,6 However, it
FROM WOLKENSTEIN’S ISOTHERM
should be noted that Eq. 共5兲 applies only for semi-infinite
homogenous semiconductors.5,6 Practically, this means that In all the numerical calculations in this work ␤ PⰆ1 was
the computational method presented in this work applies as it obtained. Therefore, Wolkenstein’s isotherm 关Eq. 共1a兲兴 may
is only for films that are thicker than the depletion layer be written approximately as ⌰⬇ ␤ P. Assuming that the fre-
width, which is typically ⬃1000 Å.6 In order to generalize it quencies ␯ 0 and ␯ ⫺ are of the same order of magnitude,4 the
for thinner films, Eq. 共5兲 should be replaced with the correct term in the first square brackets on the right-hand side of Eq.
expression for Q sc as a function of V s , taking into account 共1b兲 is approximately equal to 1. Thus, the adsorption coef-
the finite film thickness and the charge density on its other ficient ␤ may be approximated as

冋 冉 冊册
side. This expression can be obtained by solving Poisson’s
1 E F ⫺E As
equation and Gauss’s theorem with the proper boundary ␤ ⬇ ␤ 0 1⫹ exp ⫽ ␤ 0 共 1⫺ f A⫺ 兲 ⫺1 . 共A1兲
conditions.28,29 gA kT
Therefore, ⌰⬇ ␤ 0 (1⫺ f A⫺ ) ⫺1 P, and the number of chemi-
sorbed adions per unit area is
V. SUMMARY AND CONCLUSIONS N ⫺ ⫽N * f A⫺ ⌰⬇N * ␤ 0 关共 f A⫺ 兲 ⫺1 ⫺1 兴 ⫺1 P. 共A2兲
A numerical computation method for quantitative evalu- Substituting Eq. 共3兲 into Eq. 共A2兲 and using the relationship
ation of the chemisorption behavior of gases on semiconduc- (E Cb ⫺E F )/kT⫽ln(NC /ND), where N C is the effective density
tors was presented. The method enables calculating the cov- of states in the conduction band, yields
erage of neutral and charged chemisorbates and the resultant N ⫺ ⬇C 0 exp共 ⫺e 兩 V s 兩 /kT 兲 P, 共A3兲
surface band bending as a function of the environmental con-
ditions 共the gas pressure and temperature兲 and the electronic where C 0 ⫽N * ␤ 0 g A⫺1 (N D /N C )exp关(ECs⫺EAs)/kT兴. From the
properties of the semiconductor substrate 共the doping level兲 charge neutrality condition and the depletion approximation6
and semiconductor/adsorbate system 共the energy level of the we obtain eN ⫺ ⫽ 兩 Q s 兩 ⫽Q sc⬇(2 ⑀⑀ 0 N D e 兩 V s 兩 ) 1/2. Substituting
chemisorption-induced surface states兲. this relation into Eq. 共A3兲 yields
The method was applied for simulating the chemisorp- 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
tion behavior of oxygen on n-type CdS as a function of the
oxygen pressure, temperature, and doping level. This simu- where C 1 ⫽eN * ␤ 0 (2 ⑀⑀ 0 ) ⫺1/2g A⫺1 N C⫺1 exp关(ECs⫺EAs)/kT兴.
lation satisfies the expected chemisorption behavior, demon- Taking the common logarithm from both sides of Eq. 共A4兲
strating the saturation of the charged form of chemisorption gives
when the Fermi level becomes aligned with the 1.15kT log10共 e 兩 V s 兩 兲 ⫹ 共 e 兩 V s 兩 兲
chemisorption-induced surface states. As a result of the pin-
ning of the Fermi level at these states, the degree of coverage ⬇2.3kT 关 log10 C 1 ⫹log10 N D
1/2
⫹log10 P 兴 . 共A5兲
of chemisorbed adions does not exceed more than a small Taking the constant-temperature derivatives from both sides
fraction of a monolayer. of Eq. 共A5兲 yields
It was found that in depletive chemisorption the degree
of coverage of chemisorbed adions is proportional to the 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
square root of the doping level, and that the resultant surface
⬇2.3kT 关 d 共 log10 N D
1/2
兲 ⫹d 共 log10 P 兲兴 . 共A6兲
band bending increases by 2.3kT when the gas pressure in-
creases by one order of magnitude or when the doping level Finally, for e 兩 V s 兩 ⰇkT Eq. 共A6兲 may be approximated as
increases by two orders of magnitude. These relationships
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
provide simple quantitative correlations between the elec-
tronic properties of semiconductor surfaces and the environ- Equation 共A7兲 indicates that the surface band bending e 兩 V s 兩
mental conditions. This is important for understanding the 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

two orders of magnitude or when the gas pressure increases 13


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