Results in Physics 7 (2017) 13081318

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Results in Physics
journal homepage: www.journals.elsevier.com/results-in-physics

Characterization, modeling and physical mechanisms of different surface

treatment methods at room temperature on the oxide and interfacial
quality of the SiO2 film using the spectroscopic scanning capacitance
microscopy
Kin Mun Wong
Independent Researcher/Scientist, Member of the American Physical Society, MD 20740-3844, United States

a r t i c l e i n f o a b s t r a c t

Article history: In this article, a simple, low cost and combined surface treatment method [pre-oxidation immersion of
Received 3 August 2016 the p-type silicon (Si) substrate in hydrogen peroxide (H2O2) and post oxidation ultra-violet (UV) irradi-
Received in revised form 1 March 2017 ation of the silicon-dioxide (SiO2) film] at room temperature is investigated. The interface trap density at
Accepted 27 March 2017
midgap [Dit(mg)] of the resulting SiO2 film (denoted as sample 1A) is quantified from the full width at half-
Available online 31 March 2017
maximum of the scanning capacitance microscopy (SCM) differential capacitance (dC/dV) characteristics
by utilizing a previously validated theoretical model. The Dit(mg) of sample 1A is significantly lower than
Keywords:
the sample without any surface treatments which indicates that it is a viable technique for improving the
Dielectrics
Electronic properties
interfacial quality of the thicker SiO2 films prepared by wet oxidation. Moreover, the proposed combined
Oxide defects surface treatment method may possibly complement the commonly used forming gas anneal process to
Radiation effects further improve the interfacial quality of the SiO2 films. The positive shift of the flatband voltage due to
Scanning capacitance microscopy the overall oxide charges (estimated from the probe tip dc bias at the peak dC/dV spectra) of sample 1A
Surfaces and interfaces suggests the presence of negative oxide fixed charge density (Nf) in the oxide. In addition, an analytical
Surface treatments formula is derived to approximate the difference of the Nf values between the oxide samples that are
immersed in H2O2 and UV irradiated from their measured SCM dC/dV spectra. Conversely, some physical
mechanisms are proposed that result in the ionization of the SiO
species (which are converted from the
neutral SiOH groups that originate from the pre-oxidation immersion in H2O2 and ensuing wet oxidation)
during the UV irradiation as well as the UV photo-injected electrons from the Si substrate (which did not
interact with the SiOH groups). They constitute the source of mobile electrons which partially passivate
the positively charged empty donor-like interface traps at the Si-SiO2 interface.
2017 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Introduction
The importance and interest of the SiO2 film that is obtained by
the thermal oxidation of Si is due to its function as a dielectric layer
between the semiconductor and metal in numerous metal-oxide
semiconductor field-effect transistor (MOSFET) electronic devices
[13]. A consequence of the mismatch between the Si and the
SiO2 lattices essentially results in structural defects known as
interface states/traps where the major source of the electronic
interface traps is usually identified with the Pb centers due to the
dangling Si bonds near the Si-SiO2 interface [4]. Conversely, the
oxide fixed charges are associated with the defects due to the
E-mail addresses: km2002wong@yahoo.com.sg, km2002wong@gmail.com,
kmwong@kinmunwong.me
incomplete oxidized Si during oxidation and they are located near
to the Si-SiO2 interface, whereas the oxide trapped charges are due
to the trapping of the electrons or holes generated in an oxide layer
as a result of the ionizing radiation and these charges are located
within the SiO2 film [5]. Consequently, the technological operation
and electrical characteristics of the SiO2 based gate dielectrics in
the MOSFET nano-devices will be dependent on the amount of
these different types of oxide charges in the Si-SiO2 structure. In
particular, the interface traps at the Si-SiO2 interface play a much
bigger role in the overall electrical performance of the MOSFET
devices [611] since the interface defects can exchange charge
with the underlining silicon substrate by alternatively trapping
and de-trapping carriers in the substrate, which is dependent on
the position of the surface Fermi energy level (EFs) at the Si-SiO2
interface. Additionally, the performance in the MOS device applica-

http://dx.doi.org/10.1016/j.rinp.2017.03.035
2211-3797/ 2017 The Author. Published by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 K.M. Wong / Results in Physics 7 (2017) 13081318
tions and the materials electronic and optical properties are also
greatly influenced by the associated density of intrinsic defects,
as demonstrated by K. M. Wong et al. using the first principles den-
sity functional theory (DFT) calculations and confocal microscopy
measurements [12,13] that exist on the surfaces and interfaces
with the underlying substrate.
Although the characterization of the interface trap density (Dit)
of the Si-SiO2 transition region are usually performed with conven-
tional and traditional electrical methods such as the high fre-
quency Termans capacitance voltage [14], combined high-low
frequency capacitance [15], conductance techniques [16] and the
Hill-Coleman method [17]. However, recently, the Si-SiO2 interface
had also been investigated with different techniques such as using
the full width at half-maximum (FWHM) of the differential capac-
itance (dC/dV) characteristics from the scanning capacitance
microscopy (SCM) measurement [1825]. This technique has been
demonstrated as a powerful tool for the non-destructive and con-
venient in-situ monitoring of the interfacial quality of the Si-SiO2
interface without the pre-requisite necessity of metallization of
the Si-SiO2 sample as the SCM probe tip can function as the gate
electrode during the measurements [18,20]. In addition, the spec-
troscopic SCM technique can also be utilized to observe the elec-
tronic structures of solid state materials at room temperature as
demonstrated by K. M. Wong [22,24]. The basic principle where
the SCM differential capacitance (dC) signal is obtained is shown
in the 3D schematic diagram in Fig. 1 where the semiconductor
surface beneath the probe is swept from accumulation to inversion
by varying the probe tip dc bias (Vtip), and the dC signal between
the SCM probe tip and the underlying semiconductor is obtained
in response to a change in the applied probe tip dc bias (dV).
The interfacial quality of very thin SiO2 film had been previously
investigated by SCM [18,20], however thicker SiO2 film which are
useful as insulators for better current spreading effects in nitride-
based light emitting diodes [26] and as isolation structures in the
form of local oxidation of silicon (LOCOS) oxide in semiconductor
integrated circuits [5] are rarely investigated by the SCM tech-
nique. For thicker oxides, the wet oxidation process is generally
used as it has a faster oxide growth rate [27]. Recently, wet process
for the oxidation of Si is performed in some ultra large scale inte-
gration systems [28] for the miniaturization of complementary
MOS (CMOS) devices. However, the wet oxidation process usually
leads to poorer interfacial quality of the grown oxide layer (with
Fig. 1. Schematic diagram of the SCM dC/dV measurements on the SiO2 film lying on the Si substrate. The FWHM and the Vtip(peak) in the SCM measurements are also
indicated.
1309
large Dit) due to the higher density of dangling bonds at the Si-
SiO2 interface [27]. Hence, it is important to explore for simple
and low cost treatment methods at room temperature to improve
the interfacial quality of the Si-SiO2 oxide samples prepared by the
wet oxidation process.
Although many methods exist for improving the interfacial
quality of the SiO2 film prepared by wet oxidation where forming
gas anneal (FGA) above 450 C is the most commonly used method
to reduce the interface state density at the Si-SiO2 interface [29].
However, some studies suggest that there is some influence of
the SiO2 thickness on the passivation quality of the Si-SiO2 inter-
face, where thicker SiO2 layer could result in a slightly poorer Si-
SiO2 interfacial quality after the FGA [3032]. Therefore two of
the lowest cost and simplest methods to improve the Si-SiO2 inter-
facial quality of thicker oxides such as the immersion of the Si sub-
strate in hydrogen peroxide (H2O2) prior to oxidation and the post-
oxidation UV irradiation of the overlying SiO2 film on the Si sub-
strate are investigated in this manuscript. Furthermore, these
two treatment methods could possibly serve as a useful comple-
ment to the FGA process since they are performed at room temper-
ature without the use of expensive equipments or complicated
chemical process. Moreover, H2O2 is a nontoxic oxidant and its
effect on the Si-SiO2 interfacial quality had not been fully
elucidated.
In this article, the SCM dC/dV spectra (which does not require
prior metallization of the Si-SiO2 samples) are used to characterize
the interfacial quality of thicker oxide samples prepared by wet
oxidation. The samples had been treated by a combination of the
two simple surface treatment methods (H2O2 immersion and UV
irradiation) at room temperature (described in the Material and
sample preparations section). In the Theory: Analytical formulas
for estimating the various charge density from the SCM dC/dV ch
aracteristics section, from the theory of the MOS capacitor, new
equations are derived (with several approximations) to estimate
some of the other type of oxide charge density from the SCM dC/
dV spectra. The SCM dC/dV measurements and calculations of
the Dit(mg) using the SCM theoretical model subsection demon-
strates the quantification of the Dit(mg) from the FWHM of the mea-
sured SCM dC/dV spectra (using a previously validated theoretical
model [16]). Subsequently, in the Estimation and discussion of the
DNf(1B,1A,average) value for samples 1B and 1A subsection, estima-
tion of the difference in the oxide fixed charge density (DNf)
1310 K.M. Wong / Results in Physics 7 (2017) 13081318
between the samples (that are immersed in the H2O2 solution and
subjected to the UV-irradiation) from the same set of the measured
SCM dC/dV spectra (which are also used to obtain Dit(mg)) are
shown. This is followed by a discussion of the polarity of the oxide
fixed charges for sample 1A in the Polarity of the oxide fixed
charges in sample 1A with the combined surface treatment meth
od subsection. In the last subsection, some possible physical
mechanisms which are partially corroborated from the analysis
of the SCM dC/dV spectra are discussed to possibly explain the
reduction of the Dit(mg) at the Si-SiO2 interface on the (1 1 1) Si sub-
strate due to the combined surface treatment method.
Material and sample preparations
In order to investigate the oxide quality of the samples prepared
under different conditions, two p-type (1 1 1) silicon wafers
(denoted as wafers A and B) with resistivity of about 130
150 Xcm and 2040 Xcm, corresponding to the Si substrate dop-
ing concentration (Nsub) of about 1  1014 cm
3 and
5  1014 cm
3, respectively, are used for the oxide growth. Two
cleaning procedures, RCA1 and RCA2, [33] which does not attack
the Si substrate, will selectively remove the organic and inorganic
contaminants on the surfaces of wafers A and B, respectively.
After the RCA1 and RCA2 cleaning processes, wafers A and B are
separately dipped in 10% hydrofluoric acid (HF) for about 25 to 35 s
for removing the unintended native oxide layer present originally
on the two Si wafer surfaces. The HF dipping process was repeated
when necessary to ensure that no droplets of the HF solution
remain on the wafer surfaces when they are brought out of the
HF solution, which would guarantee that the native oxide layer
on the surfaces of both wafers A and B are completely removed.
Deionized water was used to rinse the two Si wafers for another
25 min and the two wafers were blown dry using dry nitrogen
(N2) gas. Both Wafers A and B were cleaved into four pieces with
a diamond scriber but only 1 piece from cleaved wafer B was used.
N2 gas was blown over the surfaces of the wafer pieces to ensure
removal of the minute particulates that remain on the broken
edges of the cleaved wafer pieces. The duration which the cleaved
pieces of wafer were exposed to the air after the 10% HF etch was
kept to a minimum before the later processing steps. Two of the
wafer pieces denoted as samples 1A and 3 (from wafer A), respec-
tively, were then immersed in the H2O2 solution for about 20 min
at room temperature, followed by blowing them dry with the N2
gas. The single piece which was cleaved from wafer B (denoted
as sample 1B) was also immersed in H2O2 for a similar duration
and blown dry with N2 gas. SiO2 layers on the bare Si surfaces of
the wafer pieces corresponding to samples 1A and 3 as well as
the other two wafer pieces (from wafer A) that had not been
immersed in the H2O2 solution (which are denoted as samples 2
and 4), were grown in a horizontal tube furnace by wet oxidation
at 650 C for about 5 h. Likewise, sample 1B was subjected to the
wet oxidation process for the oxide growth on the bare Si surface
at similar temperature and duration. (If such oxides are used in
CMOS devices, the relatively low oxidation temperature can mini-
mize dopant diffusion). The oxide thickness (tox) of the five sam-
ples grown by the wet oxidation process, as obtained from the
Table 1
The different surface treatment methods performed on samples 1A to 4 (wafer A) and sample 1B (wafer B). Their corresponding Nsub and tox values are also depicted.
Sample no. Pre-oxidation immersion of the Si substrate in H2O2
1A Yes
1B Yes
2 No
3 Yes
4 No
ellipsometry measurements are shown in Table 1, with some slight
variation of tox between the samples.
After the samples were taken out of the furnace, samples 1A and
2 that have been previously immersed and not immersed in the
H2O2 solution, respectively, prior to the wet oxidation process
were immediately irradiated with ultra-violet (UV) light. The UV
lamp was positioned about 8 cm above the samples and the UV
irradiation was performed at the wavelength (k) of about 290 nm
( 4.25 eV) with the same intensity at room temperature for a
short duration of about 10 min (to possibly reduce or minimize
the radiation induced damage of the UV irradiation on the SiO2 film
in samples 1A and 2). Similar set-up, procedures and duration of
the UV irradiation were also applied to sample 1B after the wet
oxidation process. Table 1 summarizes the different surface treat-
ment methods that were selectively applied to samples 1A to 4 and
1B.
Theory: Analytical formulas for estimating the various charge
density from the SCM dC/dV characteristics
For oxide samples with amphoteric Si-SiO2 interface states
[4,34] and when the Si Nsub is < 1  1017 cm
3 (case (b) in Ref.
[35]), when the oxide sample is biased at Vtip(peak), the semiconduc-
tor surface is close to the flatband condition [i.e. Vtip(peak) = flatband
voltage (VFB)] [35]. This is due to the relationship between the ser-
ies resistance of the semiconductor sample at different Nsub and
the difference of the capture/emission time constant of the inter-
face states [35]. However, it should be clarified that during the
dC/dV sweep, as the probe tip dc bias is varied from
10 V to
10 V, the p-type sample is swept from accumulation to inversion
[20]. Hence the flatband surface condition for samples 1A to 4
(with Nsub = 1  1014 cm
3) and sample 1B (with Nsub = 5  1014 -
cm
3) is only valid at the particular probe tip dc bias value of
Vtip(peak), as the probe tip dc bias changes from
10 V to 10 V dur-
ing the dC/dV sweep [35]. Therefore, in the subsequent discussions
of this manuscript, at the particular probe tip dc bias value of Vtip
(peak), the equation (Vtip(peak) = VFB) is valid for samples 1A to 4 and
1B.
In the presence of interface trap, oxide fixed and trapped
charges, the flatband voltage shift, VFBshift VFB
VFBideal in the
context of the SCM dC/dV spectra is given as [5] :
Q oxide
VFBshift VFB
VFBideal
1
Cox
where the ideal flatband voltage (VFB(ideal)) is defined as the work
function difference between the cobalt coated probe tip and the
p-type Si substrate (UMS) and they are expressed as :
UM US
VFBideal UMS

q q



UM vs EgSi kT Nsub



ln 2
q q 2q q ni
UM and US are the workfunction of the cobalt coated probe tip
and the p-type Si substrate, respectively, and vs is the electron
affinity of Si where the units of UM, US, vs are in eV. Eg(Si) is the
Post-oxidation UV irradiation of the SiO2 film Nsub (cm
3) tox (nm)
Yes 1  1014 32.6
Yes 5  1014 33.3
Yes 1  1014 32.1
No 1  1014 32.4
No 1  1014 32.0
 K.M. Wong / Results in Physics 7 (2017) 13081318
Si bandgap (in eV), ni is the intrinsic carrier concentration of Si, k is
the Boltzmanns constant, T is the temperature, q is the electron
charge and ln is the natural logarithm. Cox etox ox
3:9
tox
eo
is the oxide
capacitance per unit area, eox, eo are the permittivity of SiO2 and
free space, respectively. In Eq. (1), Qoxide is the overall oxide charge
per unit area which is the sum of the interface trap charge, oxide
fixed charge and oxide trapped charge per unit area (Qit, Qf and
Qot), that are located at the interface and bulk, respectively, of
the Si-SiO2 structure (Qot is defined in Ref. [5]). However, in the
context of SCM measurements, there is an additional component
consisting of the localized charge trapping in the oxide that could
sometimes occur during the SCM dC/dV measurements at the
probe tip location [Qtrap(SCM)]. Hence Qoxide is given as :
Q oxide Q it Q f Q ot Q trapSCM
Ztox   [DNf(1B,1A)], is given as (please see the SI) :
qot xx
Q it Q f dx Q trapSCM 3

tox
0 DNf1B;1A Nf1B

where qot(x) is the oxide trapped charge density per unit volume
(Ccm
3) in the SiO2 film [from the Si-SiO2 interface (denoted as
x = 0) to the top of the SiO2 film (denoted as x = tox)] due to the
UV irradiation [5]. The mobile ionic charges are neglected in this
study since RCA cleaning was used to remove the alkali-metal ions
on the Si wafer and special care was taken in the subsequent pro-
cessing steps so as not to introduce the ionic contaminants into
the Si-SiO2 samples. Although the SCM measurement introduces
an additional Qtrap(SCM) component in the VFB, however, the SCM
technique provides a direct measurement of the electronic proper-
ties of the Si-SiO2 structure without the prior metallization of the
SiO2 film. By substituting VFB = Vtip(peak) (due to the physical inter-
pretation of Vtip(peak) as discussed earlier) and VFBideal UMS from
Eq. (2) into Eq. (1), respectively. Subsequently, Eq. (1) can be
expressed for the cobalt probe tip-SiO2-Si system in samples 1A
to 4 and 1B as follows :
Q oxide
VFBshift Vtippeak
UMS
4
Cox
To obtain some new analytical expressions relating the mea-
sured parameters in the SCM dC/dV spectra to the DNf between
two UV-irradiated samples, oxide fixed charge density (Nf) and
qot, some approximations have to be made. The details of the
derivation of these equations are provided in the Supplementary
Information (SI). Using the theoretical model which had been pre-
viously validated for oxide samples grown by the wet oxidation
process (at 600 C) [18], the extracted Dit value (as discussed in
the SI) is typically close to the interface trap density at midgap
[Dit(mg)], which is given by :
Cox
Ditmg Btsp
KAtsp  5
kT
and the term K in Eq. (5) above is given by
FWHMe
FWHMi Bi tspi
K 6
G Ai tspi
where tsp and tspi are the normalized surface band bending (i.e.
surface potential) at the probe tip bias, Vtip(peak) and Vtip(peak,i) cor-
responding to the SCM experimental dC/dV peak position and the
ideal dC/dV peak position, respectively. The full expressions for
the terms A(msp) and B(msp) in Eq. (5) as well as the terms G, Ai(mspi)
and Bi(mspi) in Eq. (6) are defined in Ref. [18]. FWHMe and FWHMi
refers to the FWHM value of the experimental and ideal dC/dV
curves, respectively, where the ideal dC/dV curve is generated from
the numerical solution of the classical C-V equations [36] for a 1-
1311
dimensional MOS capacitor configuration. In addition, it should
be clarified that the SCM theoretical model used for the calculation
of Dit(mg) is only applicable for Nsub < 1  1017 cm
3. This is due to
the model equations that were used in the derivation of Eqs. (5)
and (6) are only valid when the doping density of the semiconduc-
tor is non-degenerate [18]. Hence, at the moderate doping density
of the Si substrate at 1  1014 cm
3 and 5  1014 cm
3 for samples
1A to 4 and sample 1B, respectively, that are considered in this
manuscript, Eqs. (5) and (6) are valid and applicable in obtaining
the Dit(mg) values of the samples.
For two UV irradiated samples 1A and 1B that were subjected to
the similar pre-oxidation immersion in H2O2 and by considering
that the various electronic parameters corresponding to the two
samples to be dissimilar (for instance tox1A tox1B), a more general
derived equation relating the DNf between the samples 1B and 1A

tox1B
Nf1A
tox1A


 
1 tox1B
A1A
A1B 7
q tox1A
where A1A Vtippeak;1A
UMS1A Cox1A q2 Ditmg;1A /F1A and A1B
Vtippeak;1B
UMS1B Cox1B q2 Ditmg;1B /F1B . The subscripts 1A and
1B denote the terms in the expressions of A1A and A1B that corre-
spond to samples 1A and 1B, respectively. Eq. (7) indicates that it
is suitable in obtaining the DNf between samples with relatively
minimal discrepancy in their tox and Nsub. Conversely, when the
tox of samples 1A and 1B are equal (i.e., tox1A = tox1B), Eq. (7) can
be simplified as :


1
DNf1B;1A Nf1B
Nf1A A1A
A1B  8
q
From Eqs. (7) or (8), the calculated DNf value between two UV
irradiated samples at the same intensity and duration with mini-
mal localized charging at the probe tip location can be estimated.
On the other hand, please refer to the SI for the necessary
approximations and derivation of Eqs. (S11) and (S14) for estimat-
ing the qot values (Ccm
3) (which also require obtaining the Nf
value from other techniques such as the C-V method [36]) of the
UV-irradiated samples as well as the Nf of the Si-SiO2 structure
with good quality oxide (without any UV irradiation), respectively.
It should be clarified that since this manuscript does not focus on
acquiring the Nf values obtained by other experimental techniques
or investigating the good quality oxide samples, hence Eqs. (S11)
and (S14) as derived in the SI are not used in this manuscript.
The main objective in the derivation of Eqs. (S11) and (S14) in
the SI is to open the possibility that an estimation or insights on
the other electrical parameters of the Si-SiO2 samples, could also
be obtained from the same set of the measured SCM dC/dV spectra.
For instance, Eqs. (5) and (6) are used to first determine the Dit(mg)
value from the measured SCM dC/dV spectra before using Eq. (S14)
in the SI to subsequently calculate the Nf value of the good quality
oxides (without any UV irradiation) from the same set of the mea-
sured SCM dC/dV spectra. Hence, both the Nf and Dit(mg) values can
be obtained directly for the high quality oxide samples from a sin-
gle SCM dC/dV measurement. On the contrary, due to the several
approximations that are used in the derivations of Eqs. (S11) to
(S14) in the SI, hence it must be emphasized that they only provide
a rough estimation of the electrical parameters from the measured
SCM dC/dV spectra. An accurate theoretical model for obtaining
the DNf, Nf or pot values from the SCM dC/dV spectra is beyond
the scope of this manuscript. It should also be reiterated that the
derived equations are only applicable for samples with
Nsub < 1  1017 cm
3.
1312 K.M. Wong / Results in Physics 7 (2017) 13081318

ingly large negative values for the dC/dV curves corresponding to

samples 2 to 4. The Dit at the Si-SiO2 interface causes the stretch-
out of the capacitance-voltage (C-V) curve [36] and hence the lar-
gest FWHM and Vtip(peak) values for sample 4 indicates that the Dit
at the Si-SiO2 interface is high for the as-prepared oxide sample
without any surface treatment. Although the magnitude of Vtip(peak)
may provide some indication of the overall charge densities pre-
sent in the oxide or at the oxide-semiconductor interface. How-
ever, the FWHM is a better indicator of the interfacial quality of
the Si-SiO2 interface as the polarity and magnitude of Vtip(peak) cor-
responding to the maximum dC/dV could be complicated by other
type of oxide charges (such as Nf) or by the localized oxide charg-
ing effects during the dC/dV sweep. The localized charging of the
SiO2 film could occur due to the negatively biased probe tip
(
10V 6 V tip < 0V) and positively biased probe tip
(0V < V tip 6 10V), respectively, which can induce substrate injec-
tion of holes (from the p-type Si substrate) and electrons (since
the samples are lightly doped, there are still some electrons in
n2
the Si substrate from the equation, ne N i ) [5], into the SiO2 film
sub
Fig. 2. Typical dC/dV vs Vtip curves for samples 1A to 4 where the overlying SiO2
at the probe tip location during the dC/dV sweep.
film on the p-type (1 1 1) Si substrate have undergone different surface treatment
conditions. Fig. 3 show the average and standard error of the FWHM and
Vtip(peak) values, respectively, corresponding to samples 1A to 4,
where the two horizontal error bars in the figure indicate the
Results and discussions
spread of the measured parameters (FWHM and Vtip(peak)). The dif-
ference between the two error bars is equivalent to two standard
SCM dC/dV measurements and calculations of the Dit(mg) using the
errors of the measured parameters from the SCM dC/dV spectra
SCM theoretical model
that are obtained from 10 different locations on each sample.
From Fig. 3, it can be observed that the surface treatment meth-
The SCM dC/dV sweep measurement was performed with an ac
ods (summarized in Table 1) on samples 2 or 3, have resulted in a
bias of 0.1 V at a frequency of 90 kHz using a Digital Instruments
reduction of the measured FWHM values and a positive shift of the
Dimension 3100 probe station [37] as shown in the schematic dia-
Vtip(peak) values as compared to sample 4 (without any surface
gram in Fig. 1 where the cobalt coated probe tip is in contact with
treatment). In addition, the reduction of the measured FWHM val-
the top of the SiO2 film at a particular location during the SCM dC/
ues is much larger for sample 2 as compared to sample 3. This indi-
dV measurements. To minimize the effects of any external light
cates that the improvement in the oxide interfacial quality with
source, the metallic and opaque hood over the scanning probe
the separate use of the post-oxidation UV irradiation of the SiO2
microscope was closed during the SCM measurements. The dC/
film is better as compared to the pre-oxidation immersion of the
dV versus probe tip voltage (dC/dV vs Vtip) characteristics for each
Si substrate in H2O2. Apparently, from Fig. 3, it is evident that com-
sample 1A to 4 and sample 1B was measured by sweeping the
bining the aforementioned treatment methods, denoted as the
probe tip-sample dc bias from
10 V to 10 V, at a sweep rate of
combined surface treatment method had further improved the
0.1 Vs
1, which is much larger than the typical 10 mVs
1 necessary
Si-SiO2 interfacial quality of sample 1A in terms of the measured
to establish equilibrium between the charging of the interface
FWHM and Vtip(peak) values among the different samples.
traps and the applied probe tip dc bias. The typical dC/dV vs Vtip
Fig. 4 shows the extracted average midgap interface trap den-
plot for the different oxide samples 1A to 4 (subjected to different
sity [Dit(mg,average)] and the standard error (represented by the error
surface treatment methods) are plotted together as shown in Fig. 2.
bars) of samples 1A to 4 (with different surface treatment meth-
As will be addressed in the Estimation and discussion of the
ods), that are obtained using Eqs. (5) and (6) from the FWHM val-
DNf(1B,1A,average) value for samples 1B and 1A subsection, the elec-
trical characteristics of samples 1A and 1B from the SCM dC/dV
spectra are relatively comparable, since the sample preparation
and combined surface treatment method applied on samples 1A
and 1B are exactly identical. In addition, the Nsub difference
between samples 1A and 1B (Nsub,1A = 1  1014 cm
3 and
Nsub,1B = 5  1014 cm
3) is observed to have minimal effect on the
dC/dV spectra corresponding to the two samples (this statement
will be addressed in the Estimation and discussion of the DNf
(1B,1A,average) value for samples 1B and 1A subsection). Therefore,
in this subsection, only the dC/dV characteristics of samples 1A
to 4 pertaining to the Dit(mg) are considered.
The polarity of the peak dC/dV magnitude reflects the p or n-
type nature of the underlying Si substrate where the negative sign
of the peak dC/dV magnitude as seen in Fig. 2 arises from the neg-
ative slope of the C-V curve in the depletion region for a p-type
substrate. Ten different locations across each of the four Si samples
(1A to 4) which are entirely covered with oxide were randomly
chosen for the dC/dV measurements. Fig. 2 shows the increase of Fig. 3. The average and standard error of the measured FWHM and Vtip(peak) values
the FWHM value and the shifting of the Vtip(peak) value to increas- from the dC/dV characteristics corresponding to 10 different locations on each
sample.
 K.M. Wong / Results in Physics 7 (2017) 13081318
Fig. 4. The extracted average and standard error of the Dit(mg) values obtained using
Eqs. (5) and (6) corresponding to samples 1A to 4 from 10 different locations on
each sample.
ues corresponding to 10 different locations on each sample (as
shown in Fig. 3). Similarly, Fig. 4 also shows that the separate
use of the surface treatment methods has resulted in a greater
reduction of the extracted Dit(mg,average,2) value corresponding to
sample 2 as compared to the Dit(mg,average,3) value of sample 3. This
is in good agreement with the smaller FWHM values of sample 2 as
compared to sample 3 as shown in Fig. 3. Moreover, Fig. 4 also
clearly shows that the magnitude of the extracted Dit(mg,average) val-
ues from the measured SCM dC/dV curves decreases monotonically
from sample 4 (without any surface treatment) to sample 1A (with
the combined surface treatment) which mirrors the monotonic
decrease of the FWHM values as observed from samples 4 to 1A
as shown in Fig. 3.
From the SCM theoretical model [18] which had been previ-
ously validated for oxide samples synthesized by the wet oxidation
process, the extracted Dit(mg,average,4) (over 10 different physical
locations) for the untreated sample 4 on the (1 1 1) Si substrate is
large at around 6  1013 cm
2eV
1. However, this value is much
lower than the surface density of Si atoms at 7.84 (atoms/nm2)
[38] [which is equal to 7.84  1014 (atoms/cm2)] on the (1 1 1) Si
surface. In addition, the extracted Dit(mg,average,4) for sample 4 is also
of comparable magnitude with the reported Dit values at the Si-
SiO2 interface on the (1 1 1) Si substrate that is obtained from the
MOS C-V measurements [34]. Analogous high levels of the Dit(mg)
at the Si-SiO2 interface had also been observed for oxides on the
(1 1 1) Si substrate from the other electrical and opto-electrical
measurements [3942]. In addition, it is also well known that
the Dit is dependent on the Si substrate crystallographic orienta-
tions [43], where the Dit at the Si-SiO2 interface for the (1 1 1) Si
surface is one of the highest as compared to the other different ori-
entations of the Si surface [43] (such as the (1 0 0) Si surface). This
is partially due to the high Si atom surface density (atoms/cm2) for
the (1 1 1) Si surface as compared to the other Si surfaces [43].
Hence, this translates to a high density of the surface dangling
bonds (Pb centers) which leads to high Dit at the Si-SiO2 interface
on the (1 1 1) Si surface as compared to the other Si surfaces [43].
Hence, with the use of the combined surface treatment method
in sample 1A, it is clearly observed in Fig. 4 that the extracted Dit
(mg,average,1A) value for sample 1A is significantly reduced by about
two orders of magnitude in comparison with the untreated sample
4. Therefore, this demonstrates a low cost, simple method at room
temperature (without the use of expensive equipment) for improv-
ing the interfacial quality of the oxide samples prepared by wet
1313
oxidation, hence the combined surface treatment method may be
a complement to the FGA process which is commonly performed
at elevated temperatures (> 400 C). (It is expected that the FGA
process will further reduce the Dit(mg) of the sample after the com-
bined surface treatment.)
Estimation and discussion of the DNf(1B,1A,average) value for samples 1B
and 1A
It should be clarified that the spectroscopic SCM dC/dV mea-
surements on sample 1B was performed at the same ac bias of
0.1 V (at a frequency of 90 kHz) as well as sweeping the probe
tip-sample dc bias from
10 V to 10 V (at a sweep rate of
0.1 Vs
1), that was similarly performed on the other samples 1A
to 4. In addition, ten different spatial locations on the oxide layer
of sample 1B were randomly chosen for the dC/dV measurements.
Fig. 5(a) and (b) show the typical forward (from 10 V to
10 V) and
reverse (from
10 V to 10 V) SCM dC/dV characteristics of samples
1A and 1B, respectively, where relatively minimal hysteresis is
observed between the forward and reverse dC/dV sweeps corre-
sponding to both samples 1A and 1B. This indicates that the local-
ized charging at the probe tip location in the UV-irradiated oxide
samples 1A and 1B during the SCM dC/dV measurements can be
neglected. Hence Eq. (7) is applicable to samples 1A and 1B to
determine the DNf value between the samples.
On the other hand, it is observed from Fig. 5(a) and (b) that
some of the general features of the measured dC/dV spectra corre-
sponding to samples 1A and 1B are relatively similar. For instance,
the FWHM of the forward and reverse dC/dV characteristics corre-
sponding to samples 1A and 1B are less than 1 V and there is min-
imal hysteresis between the two sets of dC/dV spectra.
Additionally, the Vtip(peak) for both samples are positive with values
close to 0 V. This indicates that the Dit(mg) values obtained using Eq.
(5) (from the FWHM), overall oxide charges per unit area obtained
using Eq. (4) [from the Vtip(peak)] and qot values (subjected to the
identical combined surface treatment method) of samples 1A and
1B are comparable. Conversely, this signifies that the difference
of the tox values (from Table 1) and Nsub between samples 1A
and 1B (1  1014 cm
3 and 5  1014 cm
3, respectively) have min-
imal effects on the dC/dV spectra of samples 1A and 1B [as shown
in Fig. 5(a) and (b) respectively]. This is in agreement with the elec-
tron spin resonance measurements which had demonstrated that
the interface states are independent of the substrate doping den-
sity [44]. Moreover, the sample preparation procedures and condi-
tions are identical for samples 1A and 1B where the combined
surface treatment method has been applied to these two samples.
Therefore the measured dC/dV spectra of sample 1B is only dis-
cussed in this subsection for the estimation of the DNf(1B,1A,average)
value between samples 1B and 1A since the electrical characteris-
tics of samples 1A and 1B from the dC/dV measurements are quite
similar. Furthermore, the polarity of the oxide fixed charges in
samples 1A and 1B can be expected to be analogous. (Further dis-
cussion on the polarity of the Nf,1A in sample 1A will be made in the
next subsection.)
The calculated Vtip(peak,average) and Dit(mg,average) values of sample
1B (over 10 different spatial locations) are 0.64 V and 7.4  1011 -
cm
2eV
1, respectively. These values are close to the correspond-
ing values of Vtip(peak,average) and Dit(mg,average) of sample 1A from
Figs. 3 and 4, respectively. Using Eq. (7), the DNf(1B,1A,average)
between samples 1B and 1A is 3.0 1010 cm
2. Consequently, Eq.
(7) when utilized on samples 1B and 1A (due to the slight tox dif-
ferences between samples 1B and 1A, hence tox1B  tox1A and tox1B/
tox1A  1) represents the difference between the average Nf1B and
Nf1A values of samples 1B and 1A. In addition, the calculated
[DNf(1B,1A,average) = Nf(1B,average)
(tox1B/tox1A)Nf(1A,average)  Nf(1B,aver-
age)
Nf(1A,average)] value of about 3.0 10
10
cm
2 indicates that the
1314 K.M. Wong / Results in Physics 7 (2017) 13081318

Fig. 5. Typical SCM dC/dV vs Vtip characteristics of the forward sweep (FS) (blue curves) and the reverse sweep (RS) (red curves) on (a) sample 1A and (b) sample 1B. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

magnitude of the average amount of Nf(1B,average) in sample 1B

(cm
2) is larger than the magnitude of the average amount of Nf
(1A,average) in sample 1A by about 3.0 10
10
cm
2. However, the
individual values of Nf1B and Nf1A cannot be determined directly
from the SCM dC/dV measurements. Conversely, from Eq. (7), the
differences or variations of Nf between different spatial locations
in a sample can be estimated when there are some differences in
the Nsub values at the different spatial locations. (For instance,
the variation in the Nf of the dielectric in the channel region of a
graded-channel transistor device.)

Polarity of the oxide fixed charges in sample 1A with the combined

surface treatment method

Unlike the oxide fixed traps, the interface states are amphoteric Fig. 6. The average and standard error of VFB(shift) and their magnitude |VFB(shift)|
where the traps in the upper half of the Si bandgap will be obtained from 10 different locations on samples 1A to 4 subjected to different
acceptor-like (negatively charged when filled with an electron surface treatment methods.

and neutral when empty) and the traps below the midgap energy
level (Emg) will be donor-like (neutral when filled with an electron
and positively charged when empty) [4,34]. Furthermore, the
charge state or occupancy of the interface traps is determined by
the EFs within the MOS structure [36]. As discussed earlier in the
Theory: Analytical formulas for estimating the various charge
density from the SCM dC/dV characteristics section, since the
p-type samples 1A to 4 are lightly to moderately doped (Nsub =
1  1014 cm
3), when they are biased in the vicinity of Vtip(peak),
the semiconductor surface is close to the flatband condition [35],
where EFs is relatively close to Emg, i.e. Emg
EFs = /F = 0.22 eV
(where /F is the Fermi potential [5]). As a result, most of the
donor-like interface traps between Emg and EFs will be unfilled
and these traps will be positively charged. Conversely, the
acceptor-like interface states in the upper half of the bandgap are
unfilled (above EFs) and hence these interface states are neutral.
In addition, the Dit obtained from Eq. (5) are expected to be close
to Dit(mg) [18]. Therefore in samples 1A to 4, the electrically charged
interface traps of the Dit(mg) are expected to consist mainly of the
positively-charged empty donor-like interface traps between Emg
and EFs.
SiO2 when exposed to the UV irradiation can create electron-
hole (eh) pairs in the SiO2 film by breaking the Si-O bonds where
the eh pairs are likely to be generated within 10 nm from the air-
SiO2 boundary (top part of the SiO2 film) [45]. However, the holes
are heavier and have a lower mobility as compared to electrons in
the SiO2 [5]. Additionally, the time constant for the relaxation of
holes from the SiO2 to the Si substrate is much larger than the time
constant for the electrons to undergo relaxation back into the Si
substrate, which is typically within the timescale of several to tens
of seconds [46]. Therefore a larger ratio of the free holes as com-
pared to electrons in the SiO2 layer will likely be trapped by the
oxide defects. These hole oxide traps could be due to different
types of defects in the thermal oxide such as the oxygen vacancies
defects (the E centers) [47]. Hence, positively charged oxide
trapped charges are possibly created in the oxide during the UV
irradiation where the polarity of Qot in sample 1A is likely to be
positive. On the other hand, from Fig. 5(a), the hysteresis between
the forward and reverse dC/dV characteristics is observed to be
negligible, hence Qtrap(SCM) = 0 in sample 1A.
From the values of Vtip(peak) as shown in Fig. 3 and Eq. (4), the
average and standard error of the VFB(shift) parameter correspond-
ing to samples 1A to 4 can be obtained as shown in Fig. 6. It is
observed from Fig. 6 that there is a positive shift of the VFB(shift) val-
ues from samples 4 to 1A and the magnitude of VFB(shift) (|VFB(shift)|)
decreases from samples 4 to 1A as shown in Fig. 6. Furthermore, |
VFB(shift,1A)| = VFB(shift,1A) for sample 1A since VFB(shift,1A) is positive.
From Eq. (4), |VFB(shift)| indicates the net amount of oxide charges
 K.M. Wong / Results in Physics 7 (2017) 13081318
per unit area in the SiO2 film and the decrease of |VFB(shift)| is in line
with the monotonic decrease of the amount of the positively-
charged donor-like Dit(mg,average) (as discussed above) from samples
4 to 1A as shown in Fig. 4.
From the above observations, some physical insights of the Nf
can be obtained from the positive and negative polarity of the
VFB(shift) values in sample 1A and samples 2 to 4, respectively. It
is necessary to clarify from Eq. (4), that a positive and negative
polarity of VFB(shift) indicates a net amount of negative and positive
charges in the SiO2 film, respectively. Therefore, the change in the
polarity of VFB(shift) from negative in samples 2, 3 and 4, to positive
in sample 1A indicates that there is a net amount of positive
charges in the SiO2 films of samples 2 to 4 and a net amount of neg-
ative charges in the SiO2 film of sample 1A, respectively.
Hence from Eq. (3), the charge polarity of the change in Qoxide,1A
(DQoxide,1A) in sample 1A is influenced by the respective charge
polarity of Nf, Dit, qot and Qtrap(SCM) in the oxide. In the earlier dis-
cussions, the charge polarity of the empty donor-like interface
traps between Emg and EFs is positive, while the charge polarity
of the oxide trapped charges is implied to be likely positive,
whereas Qtrap(SCM) = 0. However, the charge polarity of Qoxide,1A
(overall oxide charges per unit area) is negative from the positive
VFB(shift,1A) as shown in Fig. 6. Therefore, this suggests/implies that
the charge polarity of Nf,1A which is near to the Si-SiO2 interface in
sample 1A is negative. The magnitude of Dit(mg,average,1A) is the low-
est as shown in Fig. 4 and this coincides with the lowest positive
magnitude of VFB(shift,average,1A) in sample 1A (which indicates the
lowest net amount of charges among the four samples) as shown
in Fig. 6. This implies that the positively charged donor-like Dit
(mg,average,1A) is possibly compensated by the negative Nf,1A in sam-
ple 1A, resulting in a positive VFB(shift,average,1A), where this observa-
tion tends to partially support the line of reasoning that Nf,1A is
negative in sample 1A. Therefore, this suggests that the combined
surface treatment method possibly leads to the presence of nega-
tive oxide fixed charges near to the Si-SiO2 interface in sample 1A.
However, the charge polarity of the Nf corresponding to the
other samples 2 to 4 cannot be inferred/deduced from the above
discussions since the polarity of VFB(shift) is negative in samples 2
to 4 which indicates that the Qoxide in samples 2 to 4 are positive.
For example, this could imply that either the amount of negative Nf
in samples 2 to 4 are unable to compensate the larger amount of
the positively charged Dit(mg,average) in samples 2 to 4 [as compared
to the smaller amount of Dit(mg,average,1) in sample 1A] as shown in
Fig. 4; or if the polarity of Nf are positive in samples 2 to 4 where
they will not alter the negative polarity of VFB(shift) (positive Qoxide)
in samples 2 to 4.
Possible physical mechanism for the improvement of the Si-SiO2
interfacial quality due to the different surface treatment methods at
room temperature
The conduction band (CB) and valence band (VB) offsets are
3.1 eV and 4.58 eV, respectively, at the Si-SiO2 interface with
respect to the Si substrate [5]. Hence, the electrons at the CB and
the holes at the VB in the Si substrate require a threshold energy
of 3.1 eV and 4.58 eV, respectively, to be photo-injected into the
CB and VB of the SiO2. Since the samples are lightly doped, from
n2
the equation, ne N i , [5] there are still some electrons in the Si
sub
CB. Consequently, the energy of the photons emitted by the UV
lamp at 4.25 eV are sufficient to photo-inject the electrons from
the Si CB into the SiO2 CB but are insufficient to photo-inject the
holes from the Si VB into the SiO2 VB, respectively. Conversely,
the UV photon energies are able to excite the electrons in the Si
VB (from the electron-hole pairs generated at the Si VB due to
1315
the adsorption of the UV irradiation) to overcome the potential
barrier of 4.22 eV [= 3.1 + Eg(Si)] into the SiO2 CB.
On the other hand, pre-oxidation immersion of the Si substrate
in H2O2 will result in the creation of high density of neutral silicon
hydroxyl groups, silanols (SiOH) [48] on the surface and the inte-
rior of the Si substrate, particularly for the regions of the Si sub-
strate that are beneath and close to the Si surface [49,50] for
samples 1A and 3. During the wet thermal oxidation of Si, the
H2O molecules are permitted to continuously diffuse through the
existing and thickening SiO2 layer to react with the Si atoms at
the Si-SiO2 interface. Moreover, DFT calculations had shown that
the H2O molecules can readily diffuse in SiO2 [51]. Hence, addi-
tional SiOH groups (beside those already created due to the pre-
oxidation immersion in H2O2) could be created in the existing
oxide layer above the Si-SiO2 interface in samples 1A to 4 during
the wet oxidation process owing to the low formation energy of
the reaction of SiO2 with the H2O molecules (SiO2 + H2O ? 2SiOH)
[51]. In addition, some studies indicate that from the above reac-
tion due to the diffusion of H2O in SiO2, the resultant concentration
of the SiOH groups in the oxide decreases from the surface of the
SiO2 film (at the air-SiO2 surface boundary) to the Si-SiO2 interface
[52], when the Si-SiO2 interface was progressively shifted into the
Si substrate during the wet oxidation process. Subsequently, in
samples 1A and 2, the interaction of the photo-injected electrons
from the Si substrate (due to the UV irradiation) with the SiOH
groups in the oxide layer leads to the formation of negative SiO

species and the release of the neutral H atoms in the oxide
through the following reaction [53] :


SiOH e
! SiO H 9
Conversely, in samples 3 and 4 without the photo-injected elec-
trons from the Si substrate (due to the UV irradiation), the above
reaction in Eq. (9) could still occur from the Fowler-Nordheim (F-
N) tunneling [54] of electrons from the Si CB. This is due to the high
electric field at the high probe tip dc biases during the SCM dC/dV
sweep which will increase the probability of electrons tunneling
through the triangulated or narrowed portion of the SiO2 potential
barrier from the Si CB into the SiO2 CB. On the other hand, the
released neutral H atoms [from the reaction in Eq. (9)] will prefer-
entially cluster in the threefold member of the Si-O ring structures
in the SiO2 network from the molecular dynamics simulation [55].
It is also necessary to determine if the energy of the photons
from the UV irradiation of the SiO2 film is enough to ionize the
resultant SiO
species due to the reaction in Eq. (9). This can be
deduced by approximating that the amount of energy required to
remove the valence electron from the singly charged SiO
[E
R(SiO)]
is identical to the energy released when an electron is attached to
the neutral SiO to form SiO
(i.e. E
R(SiO) = electron affinity of SiO [EA
(SiO)]). By using this approximation, from the DFT calculations with
different exchange-correlation functionals, it was reported that the
values of EA(SiO) ranges from 0.08 eV to 0.76 eV [56]. Therefore, dur-
ing the 10 min UV-irradiation of samples 1A and 2, initially, the
photo-injected electrons from the Si substrate due to the UV photons
will generate the SiO
species according to the reaction in Eq. (9).
Subsequently, in the latter part of the UV irradiation, the UV photon
energy at about 4.25 eV is sufficient to free the electrons in the neg-
atively charged SiO
species in the SiO2. Additionally, from the
approximation [E


R(SiO) = EA(SiO)], the values of ER(SiO) is relatively
low due to the relatively low DFT calculated values of EA(SiO) [56],
hence the energy of the released electrons from the SiO
species
[E


R(SiO)] (= 4.25
ER(SiO)) in samples 1A and 2 will be relatively high.
Furthermore, owing to the relatively low values of E
R(SiO), hence in
samples 3 and 4, it may be possible for the SiO
species in the oxide
to behave as stepping stones for the transfer of electrons in the bulk
SiO2 to the Si-SiO2 interface by the successive correlated hops of the
electrons between the neighboring SiO
species in the oxide.
1316 K.M. Wong / Results in Physics 7 (2017) 13081318
e-
H
o e-
8.8 eV
UV
SiOH
due to the pre-oxidation
immersion in H2O2 and
ensuing wet oxidation
due to SiOH + e
Fig. 7. Schematic diagram (not drawn to scale) showing the mechanisms of the passivation of the positively-charged DLIT in sample 1A due to the combined surface
treatment method.
On the other hand, due to the lower concentrations of the SiOH
groups in the oxide in sample 2 as it was not immersed in H2O2,
hence the resultant density of the SiO
species due to the reaction
in Eq. (9) will be lower as compared to sample 1A. Consequently,
the amount of mobile electrons released by the SiO
species in
the oxide during the subsequent UV irradiation will be reduced,
even though an equal amount of electrons could be directly
photo-injected into the SiO2 CB from the Si substrate due to the
UV irradiation. This results in a reduction of the overall amount
of the generated mobile electrons from the ionized SiO
species
due to the UV irradiation in the oxide in sample 2. Conversely,
for the H2O2 treated sample 3, although there is a high concentra-
tion of silanols in the oxide. However, the amount of electrons that
could be present in the SiO2 CB due to the F-N tunneling of elec-
trons from the Si CB to generate the SiO
species in the oxide from
the reaction in Eq. (9), is much lesser than the photo-injected elec-
trons from the Si substrate due to the UV irradiation in samples 1A
and 2. This is because the F-N tunneling of electrons from the Si CB
to the SiO2 CB can only take place during the brief periods at the
high Vtip during the dC/dV sweep, whereas the photo-injection of
the electrons into the SiO2 CB during the 10 min UV irradiation
can take place in the latter part of the process. Therefore, there is
a low density of SiO
species in the oxide for the subsequent elec-
trons hopping between the SiO
species in sample 3. Similarly, for
the untreated sample 4, owing to the combination of the lower
concentration of the SiOH groups in the oxide (without the H2O2
treatment) and the smaller amount of the F-N tunneled electrons
in the SiO2 CB from the Si CB for the reaction in Eq. (9) to take place.
Hence, sample 4 will have the least density of the SiO
species
among the 4 samples for electrons hopping towards the Si-SiO2
interface. Therefore, from the above discussions, the resultant den-
sity of the mobile electrons ionized from the SiO
species is the lar-
gest in sample 1A and decreases from samples 1A to 4 due to the
different surface treatment methods.
Earlier in the Polarity of the oxide fixed charges in sample 1A
with the combined surface treatment method subsection, it was
inferred from the positive VFB(shift,1) value that the oxide fixed
charges (OFC) in sample 1A are negative. Most of the released elec-
trons from the SiO
species due to the UV photons (as discussed in
the earlier paragraphs) are rather energetic with relatively high
E(e
,SiO
) values. These energetic electrons and the smaller concen-
tration of the electrons (with high energies) that are directly
photo-injected in the upper part of the oxide (closer to the
e-
e-
3.1eV
CB
UV
e - (SiO)- 1.12 eV
Emg
(SiO)- e- 0.22eV
EF
UV
VB
4.58 eV
o Negative OFC
SiO + H
SiO2 Si
surface-SiO2 interface) from the Si substrate (due to the UV irradi-
ation), will have enough energies to overcome the repulsive
coulombic force of the negative OFC. These two groups of energetic
electrons together with the released electrons from the SiO
spe-
cies (due to the UV irradiation) that are located between the neg-
ative OFC and the Si-SiO2 interface as well as the UV excited
electrons that are directly photo-injected between the OFC and
the Si-SiO2 interface (from the Si CB), will then be able to migrate
towards the positively charged empty donor-like interface traps
(DLIT) between Emg and EFs at the Si-SiO2 interface. Fig. 7 shows
the details of the movement of these different groups of generated
mobile electrons in the SiO2 film in sample 1A.
Due to the relatively short time constant for the relaxation of
electrons in thicker SiO2 layer, which is typically within the time-
scale of several to tens of seconds [46], hence most of the gener-
ated mobile electrons in the SiO2 film in sample 1A will
eventually relax back into the bulk Si substrate. However, a smaller
portion of the generated energetic electrons moving towards the
Si-SiO2 interface to undergo relaxation back into the Si substrate
from the SiO2 dielectric could be captured by oxide traps with long
lifetime or by defects in the vicinity of the OFC, which could possi-
bly lead to a further build-up of negative OFC near to the Si-SiO2
interface in sample 1A. This is possibly substantiated by the posi-
tive VFB(shift,1A) of sample 1A which can only occur if there is a
net amount of negative charges in the oxide and the positively
charged DLIT at the Si-SiO2 interface are compensated by the neg-
ative OFC in the oxide as discussed in the Polarity of the oxide
fixed charges in sample 1A with the combined surface treatment
method subsection. Therefore, the above experimental observa-
tions may provide some support for the mechanisms (as discussed
in the earlier paragraphs) elucidating the generation of mobile
electrons due to the combined surface treatment method in sample
1A. Owing to the electric field between the negative OFC and the
positively charged empty DLIT at the Si-SiO2 interface, the gener-
ated electrons in response to the electric field will tend to drift
towards the positive DLIT at the interface instead of traveling
towards the uncharged empty acceptor-like interface traps above
Emg as well as the neutral filled DLIT below EFs. Consequently, the
larger amount of mobile electrons in sample 1A traveling to the
DLIT could possibly result in better efficiency for the subsequent
partial occupation, neutralization and passivation of the positively
charged empty DLIT between Emg and EFs at the Si-SiO2 interface
with electrons. Hence, this may significantly reduce the Dit(mg) of
 K.M. Wong / Results in Physics 7 (2017) 13081318
the Si-SiO2 interfacial layer in sample 1A. Similarly, as the amount
of generated mobile electrons is larger in sample 2 as compared to
sample 3 (as discussed earlier), hence this indicates that the sepa-
rate UV irradiation treatment of the oxide result in better Si-SiO2
interfacial quality as compared to the H2O2 surface treatment. This
is also observed from the lower Dit(mg,average,2) of sample 2 as com-
pared to the Dit(mg,average,3) of sample 3 as shown in Fig. 4.
Conclusion
SCM is a convenient method for the electrical characterization
of the interfacial quality of the SiO2 film without the pre-
requisite metallization of the Si-SiO2 samples. Hence, in this article,
the SCM theoretical model which was previously validated, is used
to quantify the Dit(mg) from the spread of the SCM dC/dV character-
istic (or FWHM), which is a measure of the interfacial quality of the
different Si-SiO2 samples that had been subjected to the different
surface treatment methods. It could be observed that both the
post-oxidation UV irradiation of the SiO2 film and the pre-
oxidation immersion of the Si substrate in H2O2 have improved
the Si-SiO2 interfacial quality of thicker oxide layers prepared by
the wet oxidation process. However, by utilizing the aforemen-
tioned treatment methods as a single combined surface treatment
method at room temperature leads to a significant reduction of the
Dit(mg,average,1A) of sample 1A by about 2 orders of magnitude as
compared to the untreated sample 4. The Dit(mg,average,4) of the
untreated sample 4 is comparable with the reported Dit(mg) values
from various electrical and opto-electrical measurements of the Si-
SiO2 structures on the (1 1 1) Si surface.
In addition, with some approximations, analytical formulas are
also derived for estimating other electrical parameters [besides
Dit(mg)] from the same set of the dC/dV spectra. For example, for
samples with slight differences in the oxide thickness and sub-
strate dopant concentrations that had been immersed in the
H2O2 solution prior to the wet oxidation process and had also been
subjected to the post-oxidation UV irradiation of the SiO2 film (at
the same intensity and duration), the difference in the Nf values
between the different samples can be estimated. Hence, additional
information besides the Dit(mg) could also be obtained from the
same set of the measured dC/dV spectra. Conversely, it is
inferred/implied from the analysis of the SCM dC/dV spectra [e.g.
Vtip(peak,1A)] and the calculated Dit(mg,average,1A) values of samples
1A, that the combined surface treatment method at room temper-
ature possibly results in negative oxide fixed charges near to the Si-
SiO2 interface. This is partially corroborated by the lowest, positive
VFB(shift,1A) magnitude of sample 1A when the probe tip dc bias cor-
responding to the measured peak dC/dV characteristics is used to
estimate the value of VFB(shift,1A).
It is proposed that in the combined surface treatment method,
the pre-oxidation immersion in H2O2 and ensuing wet oxidation
result in the creation of the neutral SiOH groups in the SiO2 layer.
During the initial phase of the UV irradiation, the interaction of the
UV photo-injected electrons from the Si substrate into the SiO2 film
convert the SiOH groups to the singly charged negative SiO
spe-
cies. Subsequently, ionization of the SiO
species in the latter
phase of the UV irradiation, together with the UV photo-injected
electrons (which did not interact with the SiOH groups) constitute
the different sources of mobile electrons. They eventually migrate
towards and could partially occupy and passivate the positively
charged empty DLIT between Emg and EFs at the Si-SiO2 interface,
hence greatly reducing the Dit(mg) in sample 1A. Therefore, from
the SCM dC/dV measurements, a simple and low cost combined
surface treatment method at the room temperature is demon-
strated for improving the interfacial quality of oxide samples pre-
1317
pared using wet oxidation, which may possibly compliment the
commonly used forming gas anneal process.
Acknowledgment
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors. Dr.
Kin Mun Wong is the corresponding author of the references
[11,22,24] and the co-corresponding author of the references
[12,13], respectively. Furthermore, Dr. Kin Mun Wong was previ-
ously (formerly) a research scientist at the Technische Universitt
Ilmenau in Germany but is currently an independent researcher/
scientist. His research interests includes computational condensed
matter physics and the application of scanning probe microscopy
and confocal microscopy for the characterization of materials. In
addition, Dr. Kin Mun Wong can be contactable at the following
email addresses : km2002wong@gmail.com, km2002wong@yahoo.
com.sg, kmwong@kinmunwong.me.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.rinp.2017.03.035.
References
[1] Hattori T, Suzuki T. Appl Phys Lett 1983;43:470.
[2] Mim NG, Kutub SB, Haque A. Results Phys. 2016;6:233.
[3] Mondol K, Hasan MM, Arafath Y, Alam K. Results Phys. 2016;6:339.
[4] Lenahan PM, Conley Jr JF. J Vac Sci Technol B 1998;16:2134.
[5] Arora N. MOSFET models for vlsi circuit simulation: theory and practice. Wien,
Austria: Springer-Verlag; 1993.
[6] Nie GZ, Zhong CL, Luo LE, Xu Y. Results Phys. 2015;5:286.
[7] Wong KM, Chim WK. Appl Phys Lett 2007;91:013510.
[8] Devaux A, Calzaferri G. Int J Photoenergy 1834;74:2009.
[9] Nicollian EH. J Vac Sci Technol 1977;14:1112.
[10] Stojadinovic N, Dimitrijev S. Microelectron Reliab 1989;29:371.
[11] Wong KM, Irfan M, Mahmood A, Murtaza G. Optik 2017;130:51724.
[12] Wong KM, Alay-e-Abbas SM, Fang Y, Shaukat A, Lei Y. J Appl Phys
2013;114:034901.
[13] Wong KM, Alay-e-Abbas SM, Shaukat A, Fang Y, Lei Y. J Appl Phys
2013;113:014304.
[14] Terman LM. Solid State Electron 1962;5:285.
[15] Castagn R, Vapaille A. Surf Sci 1971;28:157.
[16] Brews JR. Solid State Electron 1983;26:711.
[17] Hill WA, Coleman CC. Solid State Electron 1980;23:987.
[18] Wong KM, Chim WK. Appl Phys Lett 2006;88:083510.
[19] Naitou Y. Jpn J Appl Phys 2012;51:115101.
[20] Wong KM, Chim WK, Ang KW, Yeo YC. Appl Phys Lett 2007;90:153507.
[21] Xia H, Li T-X, Tang H-J, Zhu L, Li X, Gong H-M, Lu W. Sci Rep 2016;6:21544.
[22] Wong KM, Chim WK, Huang JQ, Zhu L. J Appl Phys 2008;103:054505.
[23] Kuge S, Yoshida H. J Appl Phys 2009;105:093708.
[24] Wong KM. Jpn J Appl Phys 2009;48:085002.
[25] Jiang C-S, Heath JT, Moutinho HR, Al-Jassim MM. J Appl Phys
2011;110:014514.
[26] Chang SJ, Shen CF, Chen WS, Ko TK, Kuo CT, Yu KH, Shei SC, Chiou YZ.
Electrochem Solid State Lett 2007;10:H175.
[27] Kishore KL, Prabhakar VSV. VLSI Design. New Delhi, India: I. K. International
Publishing House Pvt. Ltd.; 2010.
[28] Huang Z, Zhang J, Li M, 16th International conference on electronic packaging
technology, Changsha, China, 2015, p. 132135.
[29] Schmidt M, Lemme MC, Kurz H, Witters T, Schram T, Cherkaoui K, Negara A,
Hurley PK. Microelectron Eng 2005;80:70.
[30] Larionova Y, Harder N-P, Brendel R, 35th IEEE photovoltaic specialists
conference, Honolulu, Hawaii; 2010, p. 001207001209.
[31] Suwa T, Kumagai Y, Teramoto A, Muro T, Kinoshita T, Sugawa S, Hattori T,
Ohmi T. Electrochem Soc Trans 2012;45:453.
[32] Huang J, Radhakrishna U, Lemberger M, Jank MPM, Polster S, Ryssel H, Frey L.
Mater Res Soc Symp Proc 2011;1287. http://dx.doi.org/10.1557/
opl.2011.1144.
[33] Kern WA, Puotinen DA. RCA Rev 1970;31:187.
[34] Gray PV, Brown DM. Appl Phys Lett 1966;8:31.
[35] Wong KM, Chim WK, Yan J. Appl Phys Lett 2005;87:053504.
[36] Nicollian EH, Brews JR. MOS (metal oxide semiconductor) physics and
technology. New York, USA: Wiley; 1982.
[37] DimensionTM 3100 Manual, version 4.43C, Veeco Metrology Group, Santa
Barbara CA 93117, USA; 2003.
1318 K.M. Wong / Results in Physics 7 (2017) 13081318
[38] Zhang T, Cheng P, Li W-J, Sun Y-J, Wang G, Zhu X-G, He K, Wang L, Ma X, Chen
X, Wang Y, Liu Y, Lin H-Q, Jia J-F, Xue Q-K. Nat Phys 2010;6:104.
[39] Putnam MC, Turner-Evans DB, Kelzenberg MD, Boettcher SW, Lewis NS,
Atwater HA. Appl Phys Lett 2009;95:163116.
[40] Angermann H, Henrion W, Rseler A. Wet-chemical conditioning of silicon:
electronic properties correlated with the surface morphology. In: Nalwa HS,
editor. Silicon-based material and devices. London, England: Academic Press;
2001. p. 26798.
[41] Durmus P, Altindal S, Tataroglu A. J Optoelectron Adv Mater 2010;12:1472.
[42] Allen JE, Hemesath ER, Perea DE, Lensch-Falk JL, Li ZY, Yin F, Gass MH, Wang P,
Bleloch AL, Palmer RE, Lauhon LJ. Nat Nanotechnol 2008;3:168.
[43] Vitkavage SC, Irene EA, Massoud HZ. J Appl Phys 1990;68:5262.
[44] Poindexter EH, Caplan PJ, Deal BE, Razouk RR. J Appl Phys 1981;52:879.
[45] Upadhyaya GS, Shohet JL, Lauer JL. Appl Phys Lett 2005;86:102101.
[46] Khosru QDM, Uddin MN, Khan MR. Appl Phys Lett 1999;75:522.
[47] Feigl FJ, Fowler WB, Yip KL. Solid State Commun 1974;14:225.
[48] Afanasev VV. Internal photoemission spectroscopy: principles and
applications. Amsterdam, Netherlands: Elsevier Science; 2008.
[49] Mizuho M. Native oxide films and chemical oxide films. In: Hattori T, editor.
Ultraclean surface processing of silicon wafers. Berlin, Germany: Springer-
Verlag; 1998. p. 54358.
[50] Zhuravlev LT. Langmuir 1987;3:316.
[51] Bakos T, Rashkeev SN, Pantelides ST. Phys Rev Lett 2002;88:055508.
[52] Doremus RH. J Mater Res 1995;10:2379.
[53] Fiori C, Devine RAB, Meilland P. J Appl Phys 1985;58:1058.
[54] Lenzlinger M, Snow EH. J Appl Phys 1969;40:278.
[55] Bongiorno A, Colombo L. Ber Bunsenges Phys Chem 1997;101:1229.
[56] Brinkmann NR, Tschumper GS, Schaefer III HF. J Chem Phys 1999;110:6240.