Professional Documents
Culture Documents
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
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.
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 *
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
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
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