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Study of the Electronic Structure of Individual Free-Standing Germanium Nanodots Using

Spectroscopic Scanning Capacitance Microscopy

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2009 Jpn. J. Appl. Phys. 48 085002

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Japanese Journal of Applied Physics 48 (2009) 085002 REGULAR PAPER

Study of the Electronic Structure of Individual Free-Standing Germanium Nanodots

Using Spectroscopic Scanning Capacitance Microscopy
Kin Mun Wong

National University of Singapore, 21 Lower Kent Ridge Road, Singapore 119077
Received April 6, 2009; accepted May 20, 2009; published online August 20, 2009

High spatial resolution spectroscopic scanning capacitance microscopy (SCM) measurements at room temperature based on the
differential capacitance (d C=d V ) versus probe tip-to-substrate bias characteristics, is directly used to characterize the electronic structure
of a pyramidal and an ellipsoidal shaped germanium (Ge) nanodot (with physical sizes smaller than the Bohr exciton radius of Ge), among
the arrays of Ge nanodots fabricated on a highly doped silicon substrate using an anodic alumina membrane as an evaporation mask. The
ability to study the individual nanodots under the probe tip circumvents and isolates the statistical disorders encountered when studying
large ensembles of size-dispersed nanodots. It is demonstrated that the spectra of the positive d C=dV peaks are reflective of the
energetics of electron trapping in the quantized energy states inside the Ge nanodots. Furthermore, the spectroscopic SCM d C=dV profile
is observed to be substantially influenced by the nanodot shape where the pyramidal Ge nanodot shows three distinct shells which are
interpreted as the s-like ground state, the first excited p-like state and the second excited d-like state. On the other hand, the elliptical
deformation of the ellipsoidal Ge nanodot breaks the shell structure which significantly affects its electronic structure. Using the spacing
between the d C=d V peaks from the spectroscopic SCM measurements, an analytical expression is derived to calculate the energy
separation between the different energy states in the Ge nanodots. # 2009 The Japan Society of Applied Physics
DOI: 10.1143/JJAP.48.085002

measurements at room temperature are observed] as com-

1. Introduction
Semiconductor nanostructures known as quantum nanodots
which are articially nanostructured systems with a reduced
dimensionality, have attracted a great deal of interest as the
continuous miniaturization of the nanodots has fullled the
possibility of realizing low-dimensional systems.1) As the
optical, magnetic and electronic properties of the nanodot
can be altered through designs in its size, shape and
crystallography,2) there is wide interest in using the nanodots
for applications in nano and opto-electronics such as infrared
photo-detectors,3) room temperature single-electron transis-
tors4) and quantum dot lasers.5) One of the commonly used
synthesis technique to obtain an ordered array of germanium
(Ge) nanodots is the use of an anodic alumina membrane
(AAM) template mask.6) Other methods for fabricating the
ordered arrays of Ge nanodots include carbon predeposition
using monomethylsilane,7) selective oxidation of silicon-
germanium-on-insulator structure8) and self-assembly proc-
esses.9)
When the size of the Ge nanodot becomes comparable to
the Bohr exciton radius, quantum eects become relevant
and the nanodot begins to exhibit quantum connement
eects. Consequently, the nanodots electronic structure is
characterized by a series of discrete quantum levels (similar
to the discrete electronic structure observed in atoms), and
diers signicantly from that of the corresponding bulk
solid.2) On the other hand, another important reason of the
Ge nanodots attractiveness for potential applications in room
temperature Ge nanodot single-electron and single-hole
transistors (Ge-SETs/Ge-SHTs) is due to its smaller
carriers eective mass as compared to the corresponding
silicon (Si) nanodots, which will therefore lead to larger
energy separation of the quantized levels within the Ge
nanodots10) as compared to a Si nanodot at the same size.
Likewise, there is also less stringent requirements for the Ge
nanodots size for room temperature SETs [where periodic
Coulomb-blockade oscillations from currentvoltage (IV)


E-mail address: km2002wong@yahoo.com.sg
085002-1
pared to Si nanodots.10)
On the other hand, the use of conventional capacitance
voltage (CV) techniques,11,12) to investigate the quantum
character of an ensemble of Ge nanodots address large
ensembles of Ge nanodots with a broad distribution of
shapes, sizes and electronic states, where the previous
studies utilizing the CV techniques on arrays of Ge
nanodots require the nanodots to be inside a suitably
designed eld-eect structure.11,12) Consequently, the val-
uable information obtained on the energy level structure is
averaged over the energy levels en masse belonging to the
inhomogeneous ensemble of the nanodots12) and conse-
quently possible individual variations are obscured.
However scanning capacitance microscopy (SCM), a
promising nano-characterization metrology technique with
spatial resolution of the order of 10 nm,1315) utilizing a
platinum probe tip with a small radius of curvature
(typically 20 nm or smaller), the SCM spectroscopic
technique is able to directly investigate the local electronic
structure of a single Ge nanodot. This would enable the
properties due to the specic nanodot to be dierentiated
from the properties of the nanodot ensemble, thus providing
a more accurate assessment of the characteristics electronic
structure associated with an individual Ge nanodot. Fur-
thermore, any prior metallization of the Ge nanodot sample
is not required as the voltage biases are directly applied to
the Ge nanodot through the SCM metallic probe tip [see
the SCM measurement setup schematic in Fig. 1(a)]. The
dC=dV vs Vtip characteristics curve of a Ge nanodot is
obtained by acquiring the dierential capacitance (dC)
between the SCM probe tip and the Ge nanodot in response
to a change in the applied ac bias (dV) when the Ge
nanodot beneath the probe tip is swept from accumulation
to inversion as the probe tip dc bias (Vtip ) is varied [see
Fig. 1(a)]. Therefore the high spatial resolution capability
of the SCM technique could be suitably utilized to
characterize and provide useful information on the elec-
tronic structure of an individual Ge nanodot in the ensemble
of nanodots.
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
Differential
Capacitance
Detection
Circuitry
dC
dV
AC FWHM
SCM
Probe DC
Vtip
Ge Ge Ge
SiO2
Si
(a)
200 nm
(b)
Fig. 1. (a) Schematic diagram of the SCM measurement setup with
a typical d C=d V vs Vtip curve. (b) Scanning electron microscope
image showing a pyramidal shaped Ge nanodot (encircled in yellow)
and a smaller-sized Ge nanodot (encircled in red) among an ordered
array of Ge nanodots fabricated on a highly doped p-type silicon
substrate.
While the quantum connement eect in the Si, Ge and
GeSn nanodots and their size-dependent electronic structure
had been studied by various high spatial resolution spectro-
scopic techniques such as scanning tunneling spectroscopy
(STS) at room temperature,16,17) Fourier-transform photo-
absorption spectroscopy,18) photoemission spectrosco-
py,19,20) X-ray absorption spectroscopy,21) and the atomic
force microscopy (AFM)/Kelvin probe technique.22) How-
ever, to date no experimental investigations exist with which
can identify the changes in the electronic structure of the Ge
nanodot due to the shape of the nanodot. This is because
besides the size of the Ge nanodot, however equally
important, the shape of the nanodot also plays an important
role in determining the electronic structure as the character-
istics and magnitude of the quantum connement eects
inside the nanodot are strongly shape dependent. For
instance, studies on semiconductor nanodots using analytical
and numerical calculations showed that the optical proper-
ties of the nanodots are strongly related to their shape.23)
Therefore, it is important to experimentally investigate
changes in the geometry-induced quantum connement
eects on the energy level separation in the nanodot, due
to a change in the nanodot shape.
In this respect, SCM measurements was used for the rst
time to study the resolved electronic quantum states of
085002-2
K. M. Wong
individual Ge nanodots through the charging states in the
nanodots due to the electron resonant injection from the
conductive probe tip into the Ge nanodots, where the
discrete charging states are interpreted by considering the
electronic states of the Ge nanodots. In addition, the original
investigation which is the second novelty point in the present
research, is that Ge nanodots with distinctly dierent shapes
will lead to changes in the electronic structure of the
conned carriers, obtained from the characterization of the
nanodot by SCM, is crucial for the detailed understanding
of the electronic properties of the Ge nanodot. This will
facilitate the articial engineering of the nanodot shape
through fabrication process with the desired electronic
properties, which is of essential importance in the nanodot-
based device applications.
To elucidate this point, in this article through detailed
experiments, the high spatial resolution SCM spectroscopy
technique at room temperature is used to investigate how
distinctly dierent Ge nanodot shapes will lead to dierent
electronic structure within the nanodot. Utilizing two Ge
nanodots with physical sizes smaller than the Bohr exciton
radius of Ge (where the nanodot begins to exhibit quantum
connement eects) but of distinctly dierent shapes
(pyramidal and ellipsoidal), it is demonstrated that the
SCM spectroscopic dC=dV measurements reect the dis-
crete nature of the electronic structure in the nanodots. For
the pyramidal shaped Ge nanodot, a shell-like structure of
the dC=dV spectra is observed whereas for the Ge nanodot
with low symmetric shape, i.e., the ellipsoidal shaped Ge
nanodot, the shell-like structure is absent in the correspond-
ing spectroscopic dC=dV prole. On the other hand, based
on the spacing between the dC=dV characteristics peaks
from the spectroscopic SCM measurements, an analytical
formula that considers the size, shape of the probe tip and
the nanodot is derived for the calculation of the energy
separation between the dierent energy states in the Ge
nanodots.
2. Experimental Procedure
Prior to the deposition of the Ge nanodots on the Si
substrate, the highly doped p-type Si substrate was subjected
to thermal oxidation at 900  C to produce a layer of silicon-
dioxide (SiO2 ) on the top surface of the substrate. To
minimize any unnecessary repetitions, whenever it is
mentioned in the paper that the Ge nanodots are lying on
the Si substrate, in actual fact, there is a layer of SiO2
between the bottom surface of the Ge nanodots and the top
surface of the Si substrate [see Fig. 1(a)]. Figure 1(b) shows
the scanning electron microscope (SEM) image of the
ordered array of Ge nanodots fabricated on the highly doped
p-type silicon (Si) substrate, using an anodic alumina
through-hole membrane as a template mask during evapo-
ration. Although the width of most of the Ge nanodots
deposited on the silicon substrate is about 60 to 70 nm as
shown in the SEM image, however it is also clearly seen that
there are a few nanodots which are signicantly smaller than
the rest of the nanodots, where one of the smaller-sized
Ge nanodot is encircled in red as shown in the image.
Furthermore, the SEM image in Fig. 1(b) also shows that a
small number of the fabricated nanodots are pyramidal in
shape where one of the pyramidal shaped Ge nanodot is
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002 K. M. Wong

encircled in yellow. The dierences in the shape and sizes of 30.0 nm

the fabricated nanodots could be possibly due to some

variation in the diameter and the shape of the pores in the
AAM template, which might have occurred during the 15.0 nm

anodization process.24) Furthermore, Ge might have pro-

gressively attached onto the circumference of some of the
pore rims during the evaporation process, thus further 0.0 nm

narrowing the size of the pores in the AAM template.

Therefore using the AAM template as an evaporation mask,
this may lead to some of the deposited Ge nanodots on the
silicon substrate having a pyramidal shape. On the other 500
400
hand, the smaller-sized Ge nanodots that are deposited on
300
the Si substrate could be possibly due to the smaller pores in 200
the AAM template or the pores which could have been 0 nm 100
100 200
partially blocked (when Ge is attached to the circumference 300 400 500
0

of the pore rims during the evaporation process). (a)

Utilizing the Digital Instruments Dimension 3000 scan-
ning probe microscope with Nanoscope IIIa controller,25) 15.0 nm

AFM imaging of the Ge nanodots, operated in contact mode

were performed on dierent regions of the Si substrate to
7.5 nm
identify and locate the smaller-sized Ge nanodots. For the
AFM and SCM measurements, conductive platinum probe
tip26) with a small radius of curvature (typically 20 nm or
smaller) and where the cantilever with spring constant of 0.0 nm

2 nN/nm was used. The relatively low spring constant of

the cantilever ensures that the applied contact force do not 0
20 nm
modify the nanodot spectroscopy by local stress eects, 40
60 60
but with enough force to yield reliable and reproducible 0 20 40

capacitance data on the Ge nanodots sample. Figure 2(a) (b)

shows the location of a smaller-sized pyramidal Ge nanodot
(encircled in yellow) among the larger-sized Ge nanodots on
a scan area of 500  500 nm2 in the three-dimensional (3D) 60

AFM topography image. Subsequently, both AFM and SCM C(+ve)

imaging were simultaneously performed directly over the
spatial location of the smaller-sized pyramidal Ge nanodot
under dark conditions. Figures 2(b) and 2(c) show the 3D
AFM and the SCM images, respectively, of the pyramidal
Ge nanodot over a smaller scan area. The color scheme of
the AFM topographic image of the pyramidal Ge nanodot in
Fig. 2(b) was changed to a dierent one for better visual-
ization of the physical sizes of the nanodot. The gure shows
that the physical sizes of the pyramidal Ge nanodot, with a
height about 12 nm and the width of its base approximately
around 16 nm, is smaller than the Bohr exciton radius of Ge
(24.3 nm by Maeda et al.).27)
On the other hand, the capacitance measurement is based
on the detuning of an ultrahigh frequency resonant capaci-
tance sensor, operating at 915 MHz. The change in the Ge
nanodot capacitance corresponding to the ac bias voltage
is detected by a lock-in amplier which outputs a signal
proportional to the amplitude of oscillation in the capaci-
tance sensor output.25) Figure 2(c) shows the SCM measure-
ments on the pyramidal Ge nanodot, obtained simultane-
ously with the topographic image [Fig. 2(b)], was performed
with an ac sinusoidal signal of 0.35 V (at an ac frequency of
90 kHz) using a platinum probe tip with a radius of curvature
of about 20 nm.26) It was observed from the SCM measure-
ments that during the scanning procedure with a xed
negative dc tip bias, the pyramidal Ge nanodot was
negatively charged with electrons as the bright (light color)
spot, with the characteristics pyramidal shape in the center
085002-3
40
0
20
C(-ve)
0
0 20 40 60
nm
(c)
Fig. 2. (a) 3D AFM topographic image showing a smaller-sized,
pyramidal shaped Ge nanodot (encircled in yellow) among the larger-
sized Ge nanodots on a scan area of 500  500 nm2 . (b) 3D AFM
topographic image of the pyramidal shaped Ge nanodot on a smaller
scan area of 68  68 nm2 . The color scale indicates the size and
height of the pyramidal shaped Ge nanodot. (c) Simultaneously
obtained SCM image of the pyramidal shaped Ge nanodot on the
same scan area of 68  68 nm2 .
of the SCM image represents a positive
C signal on the
color scale. (The polarity of the
C signal is reective of the
polarity of the slope of the corresponding CV character-
istics where positive and negative
C represent electron and
hole trapping in the Ge nanodot, respectively.) Furthermore,
the sharp corners of the center bright spot in the SCM image
show that there is some correlation with the topographic
features of the pyramidal Ge nanodot. On the other hand,
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002 K. M. Wong

20.0 nm the 3D AFM and the SCM images, respectively, of the

ellipsoidal Ge nanodot over a smaller scan area where
similarly, the size of the nanodot with a height and base
10.0 nm width of about 8 nm and 22 nm, respectively, is smaller than
the Bohr radius of Ge. On the other hand, the elliptical-
shaped center bright spot in the SCM image, besides
0
0.0 nm indicating electron trapping in the nanodot, also analogously
indicates that the topographic and the SCM features of the
100
ellipsoidal Ge nanodot are correlated in the two images
200 [Figs. 3(b) and 3(c)].
300
400
500 3. Results and Discussion
nm
400 300
200 3.1 Discussion and interpretation of the spectroscopic
500
0
100 SCM d C=d V measurements on the pyramidal
(a) shaped Ge nanodot
15.0 nm
The dC=dV vs Vtip characteristics of the pyramidal Ge
nanodot was obtained by directly probing the nanodot with
the platinum probe tip. The probe tip was kept in contact
7.5 nm
with the nanodot by inhibiting the scanning motion
associated with the previous area scan [Figs. 2(a) to 2(c)],
and the dc probe tip-to-substrate bias (Vtip ), applied to the
0.0 nm pyramidal Ge nanodot, was swept from 0 to 10 V (forward
sweep) and from 10 to 0 V (reverse sweep). Figures 4(a)
Wb,el and 4(b) show the forward and reverse sweep dC=dV
0 characteristics of the pyramidal Ge nanodot at two dierent
20 60 sweep rates of 1 and 0.1 V/s, respectively. (The magnitudes
40
of the dC=dV curves in the plots are in arbitrary units.) The
40
positive dC=dV peak magnitude indicates electron trapping
nm
60 20 in the pyramidal Ge nanodot which is reective of the
0 positive gradient of the slope of the corresponding CV
(b) characteristics. The gures show that the electron trapping in
the pyramidal Ge nanodot is due to the electron injection
75
from the negatively biased platinum probe tip into the
nanodot (further explanations will be provided in 3.1.2).
C(+ve)
As the arrays of Ge nanodots (which include both the
50 pyramidal and ellipsoidal Ge nanodots) were fabricated on a
highly doped p-type Si substrate with dopant concentration
0
at 1  1020 cm3 , the substrate eect on the Ge nanodots
would be minimized during the spectroscopic SCM dC=dV
25 measurements. This can be seen from Fig. 5(a) which shows
C(-ve)
the dC=dV characteristics of the highly doped substrate
obtained by sweeping Vtip between 0 and 10 V at a sweep
rate of 0.1 V/s. It is clearly seen that the small negative, hole
0
0 25 50 75
trapping dC=dV peak magnitude (reective of the high
nm dopant concentration of the p-type Si substrate) is signi-
(c)
cantly smaller than the series of positive, electron trapping
Fig. 3. (a) 3D AFM topographic image showing a smaller-sized, dC=dV peaks corresponding to the pyramidal Ge nanodot.
ellipsoidal shaped Ge nanodot (encircled in yellow) among the larger- Furthermore, the negligible width of the hysteresis loop
sized Ge nanodots on a scan area of 500  500 nm2 . (b) 3D AFM formed between the forward and reverse sweeps of Vtip
topographic image of the ellipsoidal shaped Ge nanodot on a smaller
corresponding to the substrate as shown in Fig. 5(a) shows
scan area of 78  78 nm2 . The width of the ellipsoidal shaped Ge
nanodot, Wb,el is indicated with a blue line. (c) Corresponding SCM that there is minimal charging of the traps in the overlying
image of the ellipsoidal shaped Ge nanodot on the same scan area of SiO2 layer on the substrate, which could aect the SCM
78  78 nm2 . dC=dV measurement of the Ge nanodots.

3.1.1 Differences in the spectroscopic d C=d V

the dark SCM region surrounding the bright center spot characteristics corresponding to the larger-sized
corresponds to the highly doped p-type Si substrate. Ge nanodot and the smaller-sized pyramidal Ge
Similarly, Fig. 3(a) shows the location of the smaller- nanodot
sized ellipsoidal Ge nanodot (encircled in yellow) among the The behavior of the dC=dV spectra corresponding to the
larger-sized Ge nanodots on a scan area of 500  500 nm2 in pyramidal Ge nanodot could be understood qualitatively by
the 3D AFM topography image. Figures 3(b) and 3(c) show comparing with the dC=dV characteristics of the larger-sized
085002-4 # 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002 K. M. Wong

4000 d shell p shell s shell 0

dC/dV (Arbitary Units)

dC/dV (Arbitary Units) -500
FS -1000 FS FS
3000
RS RS RS
-1500
2000 -2000
FS -2500
RS Highly Doped
1000 -3000
P-type Substrate
-3500 Dopant Concentration ~ 1x1020 cm-3
0 -4000
-10 -8 -6 -4 -2 0
-10 -8 -6 -4 -2 0 Vtip (V)
Vtip (V)
(a)
(a)
4000
Electron Trapping
4000 d shell p shell s shell 3500

dC/dV (Arbitary Units)

in Ge nanodot of
3000 Diameter ~ 60 - 70 nm
dC/dV (Arbitary Units)

RS
3000 FS 2500
RS FS
2000
2000 1500
FS 1000

1000 RS 500
0
-10 -8 -6 -4 -2 0
0 Vtip (V)
-10 -8 -6 -4 -2 0 (b)
Vtip (V)
4000
(b)
dC/dV (Arbitary Units)

3500
Injection of 3000
Ge electrons from 2500
Native probe tip RS FS
Oxide 2000
1500
1000
Vtip < 0 SiO2
500

CB
EF
eVtip
Ge
Pt Probe
Tip VB
(c)
Fig. 4. SCM forward sweep (in blue) and reverse sweep (in red)
spectroscopic d C=d V vs Vtip characteristics of the pyramidal shaped
Ge nanodot obtained at different sweep rates: (a) 1, and (b) 0.1 V/s.
The d C=d V peaks belonging to a particular shell in the nanodot are
labeled correspondingly. (c) Schematic diagram illustrating the
corresponding filling of the energy levels/states in the Ge pyramidal
nanodot, for simplicity, the energy levels of the Si substrate are not
included in the diagram.
Ge nanodots. Figures 5(b) and 5(c) show the typical forward
sweep and reverse sweep dC=dV vs Vtip characteristics at
two dierent sweep rates of 1 and 0.1 V/s, respectively,
obtained by directly probing on a typical larger-sized Ge
nanodot (diameter around 60 70 nm). Similarly, the gures
085002-5
0
-10 -8 -6 -4 -2 0
Vtip (V)
(c)
Fig. 5. (a) SCM d C=dV vs Vtip characteristics of the highly doped p-
type silicon substrate obtained at a sweep rate of 0.1 V/s. (b,c) SCM
forward sweep (FS) and reverse sweep (RS) d C=dV characteristics
of a typical larger-sized Ge nanodot (diameter 60 { 70 nm) for
various sweep rates: (b) 1, and (c) 0.1 V/s.
show that the positive dC=dV peak is attributed to electron
trapping in the larger-sized Ge nanodot. However, there are
some signicant dierences between the spectroscopic
dC=dV characteristics corresponding to the pyramidal Ge
nanodot and the larger-sized Ge nanodot. First of all, the
magnitude of the positive (electron trapping) dC=dV peak of
the pyramidal Ge nanodot is higher than the magnitude of
the positive dC=dV peak of the larger-sized Ge nanodot.
As the dC=dV peak magnitude is inversely proportional to
the carrier concentration in the nanodot, this observation
suggests that the probe tip bias results in greater amount of
electron trapping in the larger-sized Ge nanodot, due to its
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
bigger size as compared to the smaller-sized pyramidal Ge
nanodot. In addition, there are no observable periodicities in
the dC=dV characteristics corresponding to the larger-sized
Ge nanodot as compared to the smaller-sized pyramidal Ge
nanodot, where its spectroscopic dC=dV spectra consist of a
series of dC=dV peaks with nearly but not constant peak
heights (with each of the peak height close to 4000).
However, a close examination of Figs. 4(a) and 4(b) shows
that there is a dierence of about 130 in peak height
magnitude between the highest and the lowest dC=dV peak
in the gures. These observations show that the size of the
Ge nanodot results in dierent charge trapping character-
istics in the nanodot. (The nanodot shape eects on the
dC=dV characteristics will be explained in 3.2.)
For a better understanding that the discrete dC=dV
charging peaks corresponding to the pyramidal and ellip-
soidal Ge nanodot originate from the quantum conned
states in the nanodot (to be discussed in 3.1.2) and not from
the trapping of the electrons on a surface defect site,28) it is
necessary to describe the trap eect of the defect site in the
native Ge oxide lying on the Ge nanodots. In a previous
paper,29) it was observed that the defects in the Ge native
oxide layer result in two major eects on the measured SCM
dC=dV characteristics when the scan rate decreases. Firstly,
as the scan rate decreases, the corresponding dC=dV peak
magnitude decreases which suggests that electron trapping in
the Ge nanodots increases as a lower scan rate of the probe
tip bias will lead to greater electron charging in both the
nanodot and the defects in the Ge native oxide layer. This is
due to the measured SCM dC=dV peak magnitude (gradient
of the slope of the CV characteristics) reecting the amount
of carrier concentration in the Ge nanodot and Ge native
oxide layer. Secondly, there is also a reduction in the
hysteresis between the forward and reverse dC=dV sweeps
as the scan rate decreases. This could be possibly due to a
decrease in the nonequilibrium charging, established be-
tween the applied dc bias sweep and the occupancy
(charging) of the traps in the Ge native oxide layer. At a
higher scan rate and with the presence of the traps/defects in
the Ge native oxide layer, there is a higher possibility that
equilibrium occupancy of these traps are not reached when
the surface potential is varied by sweeping of the dc bias.29)
3.1.2 Spectroscopic d C=d V peaks reflect the
energetics of electron trapping in the quantized
energy states in the pyramidal Ge nanodot
Since the physical sizes of the pyramidal Ge nanodot is
smaller than the Bohr exciton radius of Ge as seen from its
topographical image in Fig. 2(b), due to quantum conne-
ment eects, its electronic structure is composed of a series
of quantized energy levels.2) As the Ge nanodots are easily
oxidized even in mild ambient conditions (i.e., air),30) thus
the surface of the pyramidal Ge nanodot will be covered by a
layer of native oxide and hence there is a dielectric layer
between the probe tip and the nanodot. As mentioned
previously, there is a layer of SiO2 (by thermal oxidation) on
the surface of the highly doped p-type substrate where the
Ge nanodots are deposited upon. Therefore these two oxide
layers act as high potential barrier31) for electron conne-
ment in the conduction band of the pyramidal Ge nanodot as
the electrons are injected into the nanodot from the negative
085002-6
K. M. Wong
biased platinum probe tip. As Vtip is varied, the Fermi level
is shifted with respect to the quantized energy levels in the
pyramidal nanodot which leads to the sequential lling of
the dierent energy levels inside the nanodot, starting from
the lowest energy level in the nanodot. The electron
population in the nanodot increases as the probe tip negative
bias increases. [See Fig. 4(c) which schematically illustrates
the corresponding lling of the energy levels in the Ge
pyramidal nanodot, for simplicity, the energy levels of the Si
substrate are not included in the schematic diagram.]
On the other hand, the voltage bias scale, Vtip in the
dC=dV plots can be converted into an energy scale (eV)
which represents the dierent energy levels/states in the Ge
nanodot by an analytical expression to be described in a later
section. Therefore the small full-width at half maximum
(FWHM) value (about 0.5 V) of an individual dC=dV peak
in Figs. 4(a) and 4(b) represents a reasonable resolution of a
single quantized energy state in the pyramidal-shaped Ge
nanodot. In addition, the use of the small ac signal (with
amplitude of 0.35 V) in the SCM spectroscopic measure-
ments would facilitate the measurement and resolution of the
narrow dC=dV peaks (with small FWHM values). On the
contrary, as the quantum connement eects in the larger-
sized Ge nanodot are far weaker, therefore the discreteness
in the energy spectrum is not observed and hence its
measured dC=dV characteristics [as shown in Figs. 5(b) and
5(c)] would only consist of a broad dC=dV curve. On the
other hand, the near constancy of the dC=dV peak
magnitude (maxima) at dierent negative Vtip as shown in
Figs. 4(a) and 4(b) attests to the almost constant amount of
charge (electron) injection from the negatively biased
platinum probe tip into the pyramidal Ge nanodot when
Vtip is varied, which is independent of the changes in the
scan rate. This is in contrast with the larger change in the
dC=dV peak magnitude corresponding to the larger-sized
Ge nanodot as seen in Figs. 5(b) and 5(c). Therefore the
observed features which are the series of dC=dV peaks in the
dC=dV spectra [in Figs. 4(a) and 4(b)] can be attributed to
the energetics of electron trapping and the sequential lling
of the energy states in the nanodot.
As discussed earlier about the trap eect of the defect
sites, an additional important observation to be noted in the
gures which further supports the above conclusion is
discussed as follows. In Figs. 5(b) and 5(c), the decrease of
the width of the hysteresis loop formed between the forward
and reverse sweeps, from about 2.85 V at the sweep rate of
1 V/s in Fig. 5(b) to about 0.96 V at the sweep rate of 0.1
V/s in Fig. 5(c), is due to the decrease in the nonequilibrium
charging between the applied dc bias sweep and the charging
or occupancy of the traps sites32) in the larger-sized Ge
nanodot. However, no signicant changes in the hysteresis
between the forward and reverse dC=dV sweep character-
istics could be observed when the sweep rate similarly
decreases from 1 to 0.1 V/s as shown in Figs. 4(a) and 4(b)
corresponding to the pyramidal Ge nanodot. In addition,
there are only small changes in the dC=dV peaks positions of
the dC=dV spectra as shown in Figs. 4(a) and 4(b) when the
scan rate decreases from 1 to 0.1 V/s. Therefore this shows
that the electron injection from the negatively biased probe
tip into the pyramidal Ge nanodot through the Ge oxide
cause the electrons to be trapped in the Ge nanodot itself and
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
not at the defects sites in the Ge native oxide layer. Hence
the dC=dV spectra as seen in Figs. 4(a) and 4(b) reects the
electron trapping in the quantized energy states inside the
pyramidal-shaped Ge nanodot and the possibility that the
peaks originated from the surface defect/trap sites in the
nanodot can be ruled out.
As the concept of eective mass is important for materials
in the nanometer scale,10) besides the use of a small ac signal
in the measurements, the low eective mass of the
conduction band electrons at room temperature33) (me

0:036me where me is the rest mass of free electron) in the Ge
nanodot (where the electrons are injected into the nanodot
from the negatively biased probe tip), might have possibly
contributed to a slightly larger separation of the quantized
electron energy levels in the pyramidal Ge nanodot. [This
follows heuristically from the classical quantum model of a
particle in the box where the energy level separation of the
quantized levels, En
2 h 2 n2 =2m
L2 is inversely pro-
portional to the eective mass of the particle for a box of
xed dimension L.] Hence this may possibly lead to an
additional improvement in the resolution between the
dC=dV peaks as seen in Figs. 4(a) and 4(b) which reects
the energetics of electron trapping in the quantized energy
states in the nanodot.
As a result, by reducing the area of the probed surface in
order to isolate and study individual Ge nanodots under the
AFM probe tip, Figs. 4(a) and 4(b) show that it is possible to
circumvent the statistical disorders encountered by capaci-
tance measurements when studying large ensembles of size-
dispersed nanodots. Similarly, in an earlier work, Chung
et al.31) has demonstrated using conductive AFM that it is
possible to gain some knowledge of the electronic properties
of a single Ge nanodot under ambient conditions (at room
temperature).31)
3.1.3 Interpretation of the shell-like structure of the
quantized energy states in the pyramidal Ge
nanodot using the FockDarwins model
The pattern and features of the dC=dV spectra in Figs. 4(a)
and 4(b) where the dC=dV peaks appear to bunch together
into separate distinct groups can be explained by rst
describing the electronic structure of a perfectly spherical
nanodot. For a spherical nanodot, the conning potential
inside the nanodot is well approximated by a parabolic
potential,2) where the energy levels/states are degenerate
and the consecutive lling of each set of degenerate states
lead to a pronounced shell structure.34) In addition, the
energy levels of the spherical nanodot can be well described
by the classical FockDarwins model.35,36) Using the Fock
Darwins model, in the absence of magnetic eld (B 0T),
the energy states are given by En;l 2n jlj 1h !0
where n is the radical quantum number n 0; 1;
2; . . ., l is the angular momentum number l 0; 1;
2; . . . and h !0 is the quantization energy. The energy
states are degenerate with constant spacing of h !0 between
the adjacent states. On the other hand, the energy states with
the various values of the angular momentum number l are
denoted with letters according to the following scheme:
(l 0, s state), (l 1, p state), (l 2, d state), (l 3,
f state), etc. Therefore the s-like ground state which is given
by the set of quantum numbers, (n 0; l 0) is two-fold
085002-7
K. M. Wong
spin degenerate37) and the next p-like states with angular
momentum number of +1 and 1 (i.e., n 0; l 1 and
n 0; l 1) which forms the second shell are two-fold
orbital and two-fold spin degenerate in a zero magnetic
eld.37) The next d-like states with the set of quantum
numbers (n 0; l 2, n 0; l 2, and n 1; l 0)
which form the third shell, in the absence of an external
magnetic eld are three-fold orbital and two-fold spin
degenerate. In general, the degeneracy of a state with
energy, 2n jlj 1h !0 is given by 22n jlj 1, how-
ever in the presence of an external magnetic eld, the
degeneracy in the energy states exhibit a magnetic eld
dependent splitting.38)
With the description of the shell-like energy levels in a
spherical nanodot, possible reasons for the bunchiness in
the distribution of the dC=dV peaks as a function of Vtip may
be explained as follows. Although the pyramidal shaped Ge
nanodot as shown in Fig. 2(b) is not spherical, however
Brack et al. using semiclassical periodic orbit theory38) and
Reimann et al. determined using density functional theo-
ry39,40) that there are similarities in the lower shells of both
spherical and tetrahedral geometries. Furthermore, among
the dierent shapes studied, only the spherical and tetrahe-
dral geometries appear as closed-shell congurations with
similar shell closings for the lower shells.3840) To the rst
approximation, the shape of the pyramidal Ge nanodot may
be approximated by a tetrahedral as the height of the
pyramidal Ge nanodot is close to the width of its base as
shown in Fig. 2(b). Therefore the similar set of shell closings
may apply to the pyramidal nanodot. While not implying
that the energy levels of the spherical and pyramidal
geometries are exactly identical, however the theoretical
calculations3840) show that it is possible for a shell-like
structure of the energy levels to occur in a pyramidal
nanodot. Furthermore, the energetically favorable pyramidal
deformation (as an approximation to the tetrahedral defor-
mation)3840) of the connement potential inside the pyr-
amidal Ge nanodot may lead to strong shell structures.
Consequently, the consecutive lling or occupation of each
set of degenerate states may possibly explain the character-
istics shell-like structure of the dC=dV spectra observed in
Figs. 4(a) and 4(b) corresponding to the pyramidal Ge
nanodot.
Since the peaks of the dC=dV characteristics in Figs. 4(a)
and 4(b) are interpreted as reecting the trapping or
occupation of the electrons in the quantized energy levels
inside the pyramidal Ge nanodot, the separation of the
dC=dV peaks into three distinct groups reveals the lling of
three distinct shells in the pyramidal Ge nanodot. The rst
shell consists of two well-resolved peaks [at 0:39 and
0:96 V in the dC=dV characteristics as shown in Fig. 4(b)]
suggest that the twin dC=dV peaks could be attributed to the
doubly degenerate s-like ground state (in the s shell) which
is rst occupied with electrons during the initial phase of the
forward dC=dV sweep. As discussed previously, since the
pyramidal Ge nanodot may possess similar shell closings as
the spherical nanodot, the attribution of the dC=dV peaks to
a particular shell in the nanodot could be supported by the
degeneracy of the particular shell using the FockDarwins
model described earlier. Since the spectroscopic SCM
dC=dV measurements are performed in zero magnetic eld,
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002 K. M. Wong

the separation between the two dC=dV peaks in the s shell, Accidental
FS FS
which indicates the lifting of the s shell degeneracy, is not RS Subshell RS
due to the interaction with the magnetic eld. Therefore the 4000
presence of two well-resolved dC=dV peaks are a result of

dC/dV (Arbitary Units)

the splitting in the double degeneracy of the s-like ground 3000
state due to the electronelectron interaction as a conse-
quence of Coulomb repulsion.37) (This assumption will be
2000
substantiated in a later section.) On the other hand, the four
dC=dV peaks in the second shell, at larger dc tip biases are
attributed to the occupation of the rst excited p-like energy 1000
state which is fourfold degenerate. Similarly, the four well-
resolved dC=dV peaks associated with the p shell is due to 0
the electronelectron interaction where the degeneracy of
the p shell is lifted resulting in constant separation between -10 -8 -6 -4 -2 0
the four dC=dV peaks. The large separation between the rst Vtip (V)
dC=dV peak in the p shell and the second dC=dV peak in the (a)
s shell is due to the additional energy that must be supplied
from the probe tip bias to overcome the energy dierence FS Accidental FS
between the consecutive shells, before the electrons can RS Subshell RS
occupy the p-like energy state. Finally, the last two dC=dV 4000

dC/dV (Arbitary Units)

peaks after the p shell are associated with the charging of the
second excited d-like energy state in the d shell with
electrons. As Vtip was biased up to a maximum of 10 V,
consequently only the rst two (of the expected six) d-like
energy state in the d shell could be observed. Similarly, the
electronelectron interaction lifts the degeneracy of the
energy state in the d shell and resolves the two dC=dV
peaks. Therefore the electronic structure of the pyramidal
Ge nanodot is found to be atom-like with energy states
comparable to shells.
3.2 Discussion and interpretation of the spectroscopic
SCM d C=d V measurements on the ellipsoidal
shaped Ge nanodot
Figures 6(a) and 6(b) show the forward and reverse dC=dV
sweep characteristics at two dierent scan rates of 1 and
0.1 V/s, respectively, for the small ellipsoidal Ge nanodot as
shown in Fig. 3(b). Similarly, the gures show that the
positive dC=dV peak magnitudes which are nearly constant
at dierent scan rate are attributed to the energetics of
electron trapping in the quantized energy levels of the
ellipsoidal Ge nanodot, but not at the trap sites in the
nanodot. [A close examination of Figs. 6(a) and 6(b) also
shows that there is a dierence of about 120 in peak height
magnitude between the highest and the lowest dC=dV peak
in the gures.] However, the dC=dV spectra of the
ellipsoidal Ge nanodot as shown in Figs. 6(a) and 6(b), is
distinctly dierent from the dC=dV spectra of the pyramidal
Ge nanodot. First of all, it is clearly seen that there is an
absence of any recurring, constant spacing between the
dC=dV peaks in the dC=dV spectra of the ellipsoidal Ge
nanodot as shown in Figs. 6(a) and 6(b). This is in contrast
with the constant spacing observed between the dC=dV
peaks in the three shells (i.e., the s, p, and d shell) of the
dC=dV spectra corresponding to the pyramidal Ge nanodot
as shown in Figs. 4(a) and 4(b). Some possible reasons for
these features may be explained as follows.
3.2.1 Elliptical deformation of the ellipsoidal Ge
nanodot breaks the electronic shell structure
As discussed above, in a perfectly spherical nanodot with
085002-8
3000
2000
1000
0
-10 -8 -6 -4 -2 0
Vtip (V)
(b)
Fig. 6. SCM d C=dV vs Vtip forward sweep (in blue) and reverse
sweep (in red) characteristics of the ellipsoidal shaped Ge nanodot
obtained at two different scan rates: (a) 1, and (b) 0.1 V/s. The fourth
and the fifth d C=d V peaks belonging to the accidental shell in the
nanodot are circled.
parabolic connement potential, the full rotational symmetry
leads to degeneracies in the energy levels. However when
the spherical nanodot is geometrically deformed into an
ellipsoidal nanodot, the ellipsoidal deformation results in
asymmetry or deformation of the spatial connement
potential inside the nanodot. This leads to the symmetry
breaking or splitting of the degeneracies of the energy levels
previously associated with the spherical symmetry.41,42)
With the splitting of the degeneracies of the energy levels,
the shell structure associated with the spherical symmetry is
removed or becomes much less pronounced. Furthermore,
the decrease in the separation between the energy levels
which are originally in dierent degenerate groups/shells
(i.e., reduction in the intershell energy separation), as a result
of the asymmetry (deformation) of the connement potential
in the ellipsoidal Ge nanodot, further obscures the visibility
of any potential shell structure. However, this does not rule
out the possibility that at certain deformations of the
ellipsoidal Ge nanodot, accidental degeneracies of the
energy levels may still occur which leads to smaller
subshells.43) Such as, the close separation between the
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
fourth and the fth dC=dV peak in the dC=dV spectra
[Figs. 6(a) and 6(b)] might possibly suggest an occurrence
of an accidental degenerate sub-shell in the energy levels of
the ellipsoidal Ge nanodot. The close separation between the
two dC=dV peaks may be possibly due to the lifting of the
degeneracy in the accidental sub-shell as a result of the
electronelectron interaction. Therefore the quantum eects
reecting any underlying asymmetry of the conning
potential due to the physical elliptical deformation of the
nanodot becomes important, and consequently modies the
electronic structure of the nanodot.
On the other hand, theoretical calculations of the
electronic structure of a two-dimensional (2D) elliptical
nanodot by the exact diagonalization method similarly show
that the degeneracy of the energy levels is lifted with uneven
or irregular spacing between the energy levels in the
nanodot.44) This is in agreement with the dC=dV spectra
as shown in Figs. 6(a) and 6(b) of the ellipsoidal Ge nanodot
where there are no perceptible periodicities in the spacing
between the dC=dV peak positions. Therefore the absence of
a clear shell structure (except the accidental sub-shell) in the
spectroscopic dC=dV spectra of the ellipsoidal Ge nanodot
show that the electronic structure of the nanodot is strongly
dependent on the nanodot shape due to the geometry-
induced connement eect in the nanodot. The above results
also show that certain deformation of the nanodot shape or
geometry is energetically more favorable or preferred for the
formation of a shell structure in the nanodots energy levels.
For example, the shell-like characteristics structure of the
energy levels inside a spherical nanodot,34) is also observed
in the pyramidal Ge nanodot due to the pyramidal
deformation of the connement potential inside the pyrami-
dal nanodot. On the other hand, the elliptical deformation of
the connement potential inside the ellipsoidal Ge nanodot
lifts the degeneracies associated with the shell structure.
4. Analytical Expression for the Calculation of the
Energy Level Separation in the Pyramidal and
Ellipsoidal Ge Nanodot
For a quantitative analysis of the dC=dV spectra, the energy
level separation between the dierent charge states in the
nanodot can be estimated by rst making the following
assumption that most of the voltage applied to the platinum
probe tip is experienced within the Ge nanodot. This
assumption is supported by the observation that the dC=dV
peak magnitude of the p-type Si substrate in Fig. 5(a)
(reective of the high dopant concentration in the substrate)
is signicantly smaller than the series of positive, electron
trapping dC=dV peaks corresponding to the pyramidal and
ellipsoidal Ge nanodot. Following the above assumption,
since Vtip corresponding to the dC=dV peak positions are
associated with the charging of the dierent energy states in
the pyramidal and ellipsoidal Ge nanodot (as discussed in
previous sections), therefore the dierence between Vtip
corresponding to the peak positions,
Vtip,peak (in the
spectroscopic dC=dV characteristics) can be used to estimate
the energy level separation,
E between the dierent charge
states in the Ge nanodot from the following expression:



nd

E e
Vtip,peak e
Vtip,peak ; 1 Rtip 1  sin 

Vtip
085002-9
K. M. Wong
where e is the electron charge and the coecient 
nd =

Vtip is a dimensionless constant which relates the change in
the potential,
nd in the nanodot to the change in the probe
tip bias,
Vtip,peak , since in the above assumption most of the
probe tip bias voltage is experienced in the Ge nanodot.
On the other hand, it can also be safely assumed that the
change of the charge in the nanodot,
Qnd (or charge
trapping in the nanodot due to charge injection from the
probe tip), which is induced by the change in the probe tip
bias,
Vtip and the probe tip capacitance, Ctip , is mostly
captured by the Ge nanodot. Hence
Qnd Ctip
Vtip .
Conversely, since the change in the nanodot potential,

nd
Qnd =Cnd is also given as a ratio of the change in
the nanodot charge,
Qnd over the nanodot self-capacitance,
Cnd , therefore in eq. (1),
nd can be expressed as a
function of Ctip and Cnd given by

Qnd Ctip
Vtip

nd : 2
Cnd Cnd
Consequently by substituting the expression of
nd from
eq. (2), the energy level separation,
E in eq. (1), can be
written as



nd

E e
Vtip,peak e
Vtip,peak

Vtip

 3
Ctip
e
Vtip,peak :
Cnd
It must be clearly stated that although the above derivations
in obtaining eq. (3) uses only simple electrostatic consid-
eration, however importantly it is to provide a rst
approximation for a more accurate theoretical modeling of
the tip-dot-substrate; on whether the quantication of
E
from the values of
Vtip,peak using the simple analytical
expression in eq. (3) will yield calculated values of
E
which are above the thermal energy at room temperature
(25 meV). In turn, the calculations to the rst approxima-
tions may help to show a basis of plausibility for the
spectroscopic SCM dC=dV characteristics obtained exper-
imentally as shown in Figs. 4 and 6. Conversely, a more
accurate theoretical modeling of the tip-dot-substrate using a
much more complicated theory (e.g., considering the capture
cross section of electrons at dierent energy levels in the Ge
nanodot) is beyond the scope of this paper.
On the other hand, the size of the probe tip and the shape
of the Ge nanodots can be incorporated into the analytical
expression of eq. (3) as follows. Although the probe tip can
be modeled as a truncated cone with a spherical tip apex
characterized by the radius of curvature, Rtip and angular
aperture, 2, however the capacitance of the spherical tip
apex is the dominant contribution in the SCM measure-
ments.45) For a platinum probe tip, Rtip is typically smaller
than 20 nm and 2 is about 60 .26) Therefore the capacitance
of the spherical tip apex when Rtip is larger than the height of
the Ge nanodot, Hnd [about 12 and 8 nm for the pyramidal
and ellipsoidal Ge nanodot as shown in Figs. 2(b) and 3(b),
respectively] can be expressed as46)
 
Rtip 1  sin 
Ctip 2
"0 Rtip ln 1
z
  4
2
"0 Rtip ln 1 ;
Hnd
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
where "0 is the permittivity of free space and z is the distance
between the spherical tip apex and the SiO2 layer on the
surface of the underlying highly-doped p-type substrate.
Since the probe tip is in contact with the top part of the Ge
nanodot during the SCM measurements, z Hnd as shown
in eq. (4) above.
To the rst approximation, the shape of the pyramidal Ge
nanodot may be approximated as a tetrahedral where the
self-capacitance of the tetrahedron was numerically solved
by Brown47) and can be expressed in an analytical form as
shown in eq. (5)48) below,
Cnd 0:58174
"0 "ge Rnd 1:1634
"0 "ge Hnd,py ; 5
where "ge 16:0 is the relative permittivity of germanium
and Rnd is the radius of its circumscribed sphere. Since the
height of the pyramidal Ge nanodot is quite close to the
width of its base, in eq. (5), for simplicity, Rnd is taken to be
equal to half of the height of the pyramidal Ge nanodot,
Rnd Hnd,py =2.


Ctip

Epy e
Vtip,peak
Cnd,py 0:5817"ge Hnd,py

   
Ctip Rtip Kk

Eel e
Vtip,peak
Cnd,el "ge Wb,el
4.1 Calculation of the energy level separation in the
pyramidal and ellipsoidal Ge nanodot using the
derived expressions
As the derivations of the equations only take into account of
the electrostatic considerations of the probe tip and the
nanodot self-capacitance, therefore the expressions in
eqs. (7) and (8) only permit an estimation of
E. However,
the equations allow the quantication of
E from the
measured values of
Vtip,peak corresponding to the spectro-
scopic dC=dV characteristics, as well as an opportunity to
observe the inuence of the various physical parameters (e.g.,
probe tip apex radius, shape and height of the nanodot, etc.)
on the separation between the energy levels in the Ge
nanodots. On the other hand, the calculations from the
spectroscopic SCM dC=dV measurements reveal the spacing
between the dierent energy states/levels in a Ge nanodot of
a particular shape, which will lead to a better design and
engineering of the Ge nanodot shape with the desired
electronic properties. As there are only small changes in the
dC=dV peak positions of the dC=dV spectra corresponding
to the pyramidal and ellipsoidal Ge nanodot, as shown in
Figs. 4(a) and 4(b), and Figs. 6(a) and 6(b), respectively,
when the scan rate decreases from 1 to 0.1 V/s. Therefore the
calculations of
E will be performed based on the measured
values of
Vtip,peak from the dC=dV spectra measured at the
lower scan rate of 0.1 V/s [i.e., Figs. 4(b) and 6(b)].
As discussed previously, by approximating the shape
of the pyramidal Ge nanodot as a tetrahedron, the self-
capacitance can be calculated using eq. (5). From the
constant interaction model,50) the electronelectron interac-
tion can be approximated in a simple way by the Coulomb
charging energy,37) which for the pyramidal Ge nanodot is
given as EC,py e2 =Cnd,py . Substituting the nanodot self-
capacitance from eq. (5) into the above equation, the
085002-10
K. M. Wong
On the other hand, the shape of the ellipsoidal Ge nanodot
may be approximated as an elliptical disc along its minor
axis (height of the nanodot) where the self capacitance of the
elliptical disc is given in eq. (6)49) as shown below:
4
"0 "ge b 2
"0 "ge Wb,el
Cnd ; 6
Kk Kk
where Kk is the complete ellipticalp
function of
the rst kind
p with modulus [k 1  a=b2
2
1  Hnd,el =Wb,el ], a is the semi-minor axis of the
elliptical disc and is taken to be equal to half of the height
of the ellipsoidal Ge nanodot a Hnd,el =2, b is the semi-
major axis where it is taken to be equal to the half of
the width of the base of the ellipsoidal Ge nanodot
b Wb,el =2.
Substituting the expression of the nanodot self-capaci-
tance from eqs. (5) and (6) into eq. (3),
E (in the units of
eV) of the pyramidal and ellipsoidal Ge nanodot is given by
eqs. (7) and (8), respectively, as
 
Rtip Rtip 1  sin 
ln 1 e
Vtip,peak ; 7
Hnd,py

Rtip 1  sin 
ln 1 e
Vtip,peak : 8
Hnd,el
calculation yields a theoretical estimate of the charging
energy to be about 27 meV. On the other hand, in the s shell
of the dC=dV spectra corresponding to the pyramidal Ge
nanodot as shown in Fig. 4(b), the dierences between the
dc tip biases corresponding to the two dC=dV peaks is about
0.57 V. Therefore the estimated energy spacing between the
two s-like ground states using eq. (7) for the pyramidal Ge
nanodot (which is also known as the single and doubly
charged nanodot ground state),
Es{s is about 61 meV. Part
of the discrepancy between the two values may possibly
originate from some additional dispersed capacitances in the
probe tipnanodot conguration or by dielectric screening.
The other reason could be due to the analytical expression in
eq. (7), which only allows an estimation of the value of

Es{s from the SCM measurements.
The discrete uctuation of the tunneling current in
individual Ge nanodots, observed with STS measurements
at room temperature had been used to determine the single-
electron Coulombic charging energy, EC in the nanodots.
For example, STS measurements performed on Ge nanodots
show that the EC values for the Ge nanodots with sizes
ranging from 2 to 3.2 nm, is about 250 to 100 meV,
respectively.16) On the other hand, the value of
Es{s 
61 meV (separation between the doubly degenerate s-like
ground states which is hypothesized to be due to the
electronelectron Coulomb interaction) from the SCM
measurements corresponding to the pyramidal Ge nanodot
(with a size of about 12 nm), is lower than the experimen-
tally obtained values of EC from 250 to 100 meV, corre-
sponding to nanodot sizes from 2 to 3.2 nm using the STS
measurements.16) As the Coulombic charging energy of the
nanodots decreases when the size of the nanodot increases,
therefore importantly this shows that the value of
Es{s
obtained from the SCM measurements, does not contradict
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
the value of EC obtained experimentally from the STS
measurements on Ge nanodots of smaller sizes (from 2 to
3.2 nm).
On the other hand, the STS measurements performed on
Ge1x Snx nanodots (x 0:10 { 0:13), where the experimen-
tally obtained values of EC corresponding to the range of
nanodot sizes from 4 to 35 nm,17) could also be used for a
comparison with the value of
Es{s corresponding to the
pyramidal Ge nanodot. As the gap width in the dierential
conductance, dI=dV curves of the STS measurements
besides indicating the energy bandgap of the nanodot, also
includes the value of EC .17) Hence for the Ge1x Snx nanodots
with sizes close to the pyramidal Ge nanodot, the average
tunneling current uctuations for those nanodots indicates
that the value of EC from the STS measurements is about
100 meV.17) Consequently, this shows that the value of

Es{s  61 meV obtained from the SCM measurements on
the pyramidal Ge nanodot is consistent with the values
obtained from the STS measurements.
Conversely, as the Coulomb charging energy is given by
(EC e2 =Cnd ) where the nanodot self-capacitance is propor-
tional to the size of the nanodot, therefore the charging
energy is inversely proportional to the size of the nanodot.
Hence for a nanodot which is about half the size of the
Ge pyramidal nanodot, it would have a charging energy
which is about twice as large. As a result, the value of

Es{s  61 meV using eq. (7) compares reasonably well
with the room temperature IV measurements on Ge-
SETs,10) where the average size of the Ge nanodot is about
6.2 nm10) (about half the size of the pyramidal Ge nanodot)
and its ground-state electron charging energy is about
125 meV10) (about twice that of the pyramidal Ge nanodot).
Therefore the calculations suggest that the origin of the split
in the doubly degenerate s-like ground states as shown in
Fig. 4 could be due to the electronelectron Coulomb
interaction.
Similarly, in Fig. 4(b), the separation between the dc tip
biases corresponding to the dC=dV peaks in the p and the d
shells is about 0.47 and 0.43 V, respectively. Using eq. (7),
the estimated energy spacing between the four p-like states,

Ep{p and between the two d-like states,
Ed{d is about 51
and 46 meV, respectively. The calculations show that the
splitting within the rst excited p-like states and within the
second excited d-like states is in even closer agreement with
the calculated Coulomb charging energy of 27 meV for the
pyramidal Ge nanodot. Therefore the lifting of the degen-
eracies of the rst excited p-like states and the second
excited d-like states could also be attributed to the electron
electron Coulomb interaction eect. However, the calcula-
tions show that the energy spacing within the p and the d
shell is quite close (i.e.,
Ep{p 
Ed{d ) but is smaller than

Es{s . This could be possibly due to the increase in the
spatial dimension of the wave functions in the excited states
(more extended in space) as compared to the ground state.51)
Therefore the electrons occupying the same excited state
will be further apart and the increased distance between the
electrons will decrease the Coulomb interaction energies as
seen from the above calculations.
On the other hand, the intershell energy separation
between the s and the p shell,
Ep{s(sh) could be calculated
from the spacing between the dc tip bias corresponding to
085002-11
K. M. Wong
the last dC=dV peak in the s shell and the dc tip bias
corresponding to the rst dC=dV peak in the p shell, which
is about 3.86 V. From eq. (7),
Ep{s(sh) is about 418 meV
and similarly the energy separation between the p and the d
shell,
Ed{p(sh) is about 309 meV. However, it is to be noted
that part of the calculated values of
Ep{s(sh) and
Ed{p(sh)
include the electronelectron interaction energy between the
electrons in the s and the p shell, and between the electrons
in the p and the d shell, respectively. Unfortunately, these
interaction energies could not be independently obtained
from the dC=dV spectra as shown in Figs. 4(b) and 6(b).
Nonetheless, the above calculated values where (
Ep{s(sh)
and
Ed{p(sh) > EC,py ) show that the intershell energy
separation is mainly due to the spatial quantization energy
as a result of the quantum connement eects (as the
physical sizes of the pyramidal Ge nanodot is smaller than
the Bohr exciton radius of Ge) rather than the Coulomb
charging energy. Importantly, all the calculated energy
separations show that they are larger than the thermal
energy, kT  25 meV at room temperature (avoiding ther-
mal perturbation).
Similarly, the self-capacitance of the ellipsoidal Ge
nanodot can be calculated using eq. (6) [where Hnd,el
8 nm, Wb,el 22 nm for the nanodot, therefore k 0:932
and using the tabulated tables,52) K0:932  2:461]. Like-
wise from the expression, EC,el e2 =Cnd,el , the theoretical
estimate of the Coulomb charging energy of the ellipsoidal
Ge nanodot is about 21 meV. Utilizing the dierences
between the dc tip biases corresponding to the dC=dV peaks
in Fig. 6(b) as well as eq. (8), the energy spacing between
the dierent energy states of the ellipsoidal Ge nanodot can
be similarly determined. The calculations show that the
energy separation between the fourth and the fth dC=dV
peak in the dC=dV spectra [Fig. 6(b)] (suspected to be an
accidental degenerate sub-shell for this particular elliptical
deformation of the ellipsoidal Ge nanodot due to the small
separation between the two peaks) is about 59 meV. This
value is larger than the theoretical estimate of the Coulomb
charging energy of 21 meV and the thermal energy at room
temperature. Part of the discrepancy between the values
might have been due to an additional shape contribution to
the energy splitting as the separation of the energy levels is
modied for the nonspherical shape.41,42) On the other hand,
Fig. 7 shows the electronic structure in the pyramidal and
the ellipsoidal Ge nanodot using the calculated energy
separation between the dierent energy states/levels [from
eqs. (7) and (8)]. In the gure, the reference of energy
(0 meV) is taken at the rst dC=dV peak in Figs. 4(b) and
6(b), which corresponds to the lling or occupation of the
electronic ground state of the nanodot.
5. Conclusions
In conclusion, spectroscopic SCM based on the dC=dV
versus Vtip characteristics is used for the rst time to
investigate/study the electronic structure of individual Ge
nanodots with distinctly dierent shape. The dierences in
the obtained electronic structure for the Ge nanodots are
interpreted in terms of the dierent shape of the dots
(pyramidal and ellipsoidal) where the electronic structure
of the pyramidal Ge nanodot shows a pronounced shell
structure. On the other hand, the elliptical deformation of
# 2009 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 48 (2009) 085002
Pyramidal Ellipsoidal
1000
800
Energy (meV)
600
400
200
0 20) Y. Nakayama, K. Takase, T. Hirahara, S. Hasegawa, T. Okuda, A.
Shape of the Ge Nanodot
Fig. 7. Electronic structure of the pyramidal and the ellipsoidal
shaped Ge nanodot.
the ellipsoidal Ge nanodot breaks the shell structure and
signicantly aects its electronic structure. Using the
spacing between the dC=dV peaks from the spectroscopic
SCM measurements, the energy separation between the
dierent energy states in the Ge nanodots are calculated with
a derived analytical expression that considers the size, shape
of the probe tip and the nanodot. Therefore the results show
that SCM with its high spatial resolution of 10 nm, is a
viable and useful nano-characterization tool for obtaining
the electronic structure in a single Ge nanodot. This is of
extreme importance and interest due to the potential
applications of the Ge nanodots in the eld of nanotechnol-
ogy, e.g., in quantum computing devices.
Acknowledgments
The author would like to thank L. Zhu for preparing the
AAM template mask and the deposition of the Ge nanodots
using the mask, on the highly doped Si substrate with an
overlying thermal oxide (provided by the author). The work
in this article was performed at the National University of
Singapore in 2008.
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# 2009 The Japan Society of Applied Physics