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Microstructural, chemical bonding, stress

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Article in Journal of Nanoparticle Research · February 2011

DOI: 10.1007/s11051-010-0054-8

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J Nanopart Res
DOI 10.1007/s11051-010-0054-8

RESEARCH PAPER

Microstructural, chemical bonding, stress development

and charge storage characteristics of Ge nanocrystals
embedded in hafnium oxide
S. Das • R. K. Singha • S. Manna •
S. Gangopadhyay • A. Dhar • S. K. Ray

Received: 19 April 2010 / Accepted: 31 July 2010

Ó Springer Science+Business Media B.V. 2010

Abstract We have grown Ge nanocrystals (NCs) Introduction

(4.0–9.0 nm in diameter) embedded in high-k HfO2
matrix for applications in floating gate memory Nanocrystal floating gate devices are attractive due to
devices. X-ray photoelectron spectroscopy has been their potential applications in next generation inte-
used to probe the local chemical bonding of Ge NCs. grated flash memories. In these devices, metal or
The analysis of Ge–Ge phonon vibration using Raman semiconductor nanocrystals (NCs) are embedded as
spectroscopy has shown the formation of compres- charge-storage nodes in an oxide layer between the
sively stressed Ge NCs in HfO2 matrix. Frequency control gate and the tunneling layer to replace the
dependent electrical properties of HfO2/Ge-NCs in continuous floating gate layers in conventional flash
HfO2/HfO2 sandwich structures have been studied. An memories (Hanafi et al. 1996; Hori et al. 1992). The use
anticlockwise hysteresis in the capacitance–voltage of NCs as floating gates offers smaller operating
characteristics suggests electron injection and trapping voltages, better endurance characteristics and faster
in embedded Ge NCs. The role of interface states and write/erase speeds as compared to conventional flash
deep traps in the devices has been thoroughly exam- memories (Hanafi et al. 1996; Kim et al. 2003a; Blauwe
ined and has been shown to be negligible on the overall 2002). Semiconductors as well as metals such as Si,
device performance. Ge, SiGe, Ni, Au and Ag have been considered as
promising candidates for the charge storage nodes in
Keywords X-ray photoelectron spectroscopy  nanocrystal floating gate devices (Hanafi et al. 1996;
Raman spectroscopy  Germanium nanocrystals  Hori et al. 1992; Kim et al. 2003a; Blauwe 2002; Choi
Charge injection et al. 2002; Das et al. 2004; Park et al. 2006; Tan et al.
2005; Wang et al. 2007). Due to the smaller band-gap,
superior carrier mobilities and higher excitonic Bohr
radius compared to Si, Ge NCs are considered to be
S. Das  R. K. Singha  S. Manna  A. Dhar  ideal nodes for use in complementary metal-oxide-
S. K. Ray (&)
semiconductor compatible memory circuits. They can
Department of Physics and Meteorology, Indian Institute
of Technology Kharagpur, Kharagpur 721302, India be embedded in a high-k dielectric, which acts as the
e-mail: [email protected] control oxide of a memory device with enhanced gate
coupling to the tunneling oxide, resulting in an
S. Gangopadhyay
enhancement of memory window at a lower program-
School of Physics and Astronomy,
University of Nottingham, University Park, ming voltage (Compagnoni et al. 2003). Ge NCs
Nottingham NG7 2RD, UK embedded in Hf-based dielectrics, one of the most

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 J Nanopart Res

attractive and promising high-k dielectrics, have been thermal annealing in nitrogen ambient at 800 and
studied only recently (Chen et al. 2005; Zhang et al. 900 °C for 30 min.
2006; Das et al. 2007b). Being physically much thicker High-resolution transmission electron microscopy
than SiO2, the leakage current of HfO2 is several orders (HRTEM) was carried out using a JEM 2100F (JEOL)
of magnitude smaller than SiO2 for the same equivalent field emission system with an operating voltage of
oxide thickness (EOT) (Lee et al. 2000), resulting in 200 kV to study the micro-structural properties of Ge
superior data retention behavior. On the other hand, NCs in the trilayer structure. X-ray photoelectron
HfO2 can provide a larger tunneling current than SiO2 spectroscopy (XPS) was used to probe the chemical
during program operation, due to the lower electron bonding of the deposited films. XPS data was acquired
barrier height of HfO2 (1.2 eV) (Zhu et al. 2002) as using a SCIENTA ESCA 300 photoelectron (Al Ka
compared to SiO2 (3.1 eV). radiation) spectrometer with an energy resolution of
Capacitance–voltage (C–V) measurement of mem- 0.4 eV using a pass energy of 150 eV and slit width
ory capacitors has been an attractive method for 0.8 mm. Lower energy electrons (\3 eV) were sup-
obtaining device characteristics due to the ease of plied from a flood gun to prevent the charging. Raman
experimental setup and data analysis. However the spectra of the sample was obtained with a Renishaw
conductance–voltage (G–V) characteristics of metal– Raman microscope equipped with a He–Ne laser
oxide–semiconductor (MOS) capacitor is known to excitation source emitting at a wavelength of
provide information directly related to the energy 632.8 nm and a Peltier cooled (-70 °C) charge-
loss, in response to the applied ac signal, during the coupled device (CCD) camera. The holographic
capture and emission of carriers by interface traps. grating (1,800 grooves/mm) and the slit provided a
Recently, a few groups (Huang et al. 2003; Ng et al. spectral resolution of 1 cm-1. The electrical properties
2006) have reported energy loss by NCs during of the trilayer structure were carried out using fabri-
G–V measurements of memory capacitor. In this cated Al-gate (area: 1.96 9 10-3 cm2) MOS capacitor
article, we present a detailed investigation of the with programmable Keithley-590 C–V analyzer,
charging, discharging and charge-retention behaviors Keithley-485 pico-ammeter and Advantest-R6144 con-
in a trilayer HfO2/Ge-NCs-embedded HfO2/HfO2 stant dc voltage source. The C–V measurement of MOS
sandwiched memory capacitor using C–V and capacitor at different frequencies was performed using
G–V measurements. The stress developed within the a HP 4294A LCR meter.
Ge NCs during solidification has been estimated by
Raman spectroscopy.
Results and discussion

Experiment Microstructural studies

The memory structures used in this study was MOS The microstructural property of Ge nanocrystal
capacitors with a dielectric stack consisting of Ge floating gate memory device was studied using
NCs sandwiched between tunneling and capping cross-sectional HRTEM. Figure 1a shows a cross-
layers of HfO2. P-type (100) Si substrate with sectional micrograph of sample annealed at 800 °C
resistivity 7–14 ( cm was initially cleaned by Piranha for 30 min in N2 atmosphere. The dark patches are
process followed by dipping in dilute HF for 1 min to Ge NCs of 4–6 nm diameters in the HfO2 matrix. The
remove the native oxide from the surface. First, a thin NCs are almost spherical and are well dispersed in
tunneling layer of HfO2 (*4 nm) was deposited on the HfO2 matrix. Figure 1a also suggests clustering of
Si by rf magnetron sputtering technique from a 3 inch neighboring NCs in annealed sample. Figure 1b
diameter HfO2 (99.999% pure) target at 50 W rf shows the TEM micrograph of a sample after
power for 8 min in Ar ? O2 ambient. The interme- annealed at 900 °C for 30 min. It shows Ge NCs
diate layer was then deposited by co-sputtering of with diameters 6–9 nm. Inset of Fig. 1b shows one
HfO2 and Ge for 30 min under the same condition such NC with clear lattice fringe. Note that there are
followed by the deposition of a final cap layer for few bigger clusters in Fig. 1b. Since the change in
40 min. The trilayer structure was then subjected to Gibbs free energy (DG) of the formation of GeO2

123
J Nanopart Res

Fig. 1 Cross-sectional
TEM micrograph of Ge
NCs embedded in HfO2 for
a 800 °C and b 900 °C
annealed sample

(-111.8 kcal/mol) is smaller than that of HfO2 Ge(111)

(-260.1 kcal/mol), DG is negative in solid reaction
of GeO2 ? Hf ? HfO2 ? Ge. Hence, the mixture of

Intensity (arb. units)

HfO2 and Ge has the lower Gibbs free energy in the
Ge(220)
co-sputtered film, resulting in the oxidation of Hf and Ge(311)
o
agglomeration of Ge atoms into NCs in HfO2 matrix. 900 C

The crystallization of all the films was investigated

by X-ray diffraction (XRD) under grazing incidence. o
800 C
Figure 2 shows the XRD pattern of as deposited and
annealed samples. The as-deposited sample has a
broad scattering peak indicating its amorphous as deposited
nature. Three peaks in both the annealed samples
marked as (111), (220) and (311) in Fig. 2 correspond
to the Bragg reflection of randomly oriented crystal- 20 30 40 50 60 70
2 degree)
lites of Ge FCC structure. The broadening of the
Bragg peak depends upon the crystallite size, strain Fig. 2 X-ray diffraction pattern of as deposited and annealed
and instrumentation broadening. The strain for the samples
two annealed samples being different, it is very
difficult to estimate the average crystallite size from *32.2 eV, respectively. The shift of the Ge 3d
only two data points, although instrumentation peak (with respect to Ge0) has been attributed to the
broadening can be deconvoluted. For annealed sam- formation of Ge–O, Ge–Hf–O and Ge–Hf bonds, as
ples, germanium suboxides phases were present along shown in the study of the Ge sub-oxides (Pourtois
with Ge cubic phase. We have not found any XRD et al. 2008; Renault et al. 2007) and Ge/HfO2
peak related to HfO2 phase. interface (Molle et al. 2006). The background of
XPS spectrum in Figure 3 has been removed using a
Chemical bonding of Ge nanocrystals linear subtraction method and fitted by three
Gaussian peaks at energy positions in agreement
Figure 3 shows a typical Ge 3d X-ray photoelectron with the literature (Renault et al. 2007). The first
spectrum of the 900 °C annealed trilayer structure one is assigned to the metallic Ge (Ge0) around the
after 23 nm of sputter etching of the film. Five binding energy 28.8 eV, and other two are oxide
oxidation states, Gen? (n = 0–4) responsible for the components of Ge. The peak shifted by 1.6 eV with
Ge 3d XPS peak could exist in Ge-embedded respect to Ge0 is related to Ge atoms in a 2?
oxides. Ge 3d XPS peaks from elemental Ge (Ge0) oxidation state (GeO) and the other is assigned to
and GeO2 are usually observed at *29 and Ge atoms in a GeO2-like environment with 3.4 eV

123
 J Nanopart Res

asymmetric broadening in the lower wave number due

GeO2 to phonon confinement. However, the blue shift of the
peak position with respect to that of the bulk reference
XPS Intensity (arb. units)

spectrum is in disagreement with the prediction of

phonon confinement theory. A similar blue shift of
Raman spectra of silica-embedded (Sharp et al. 2005;
Ge-O Wellner et al. 2003) and sapphire-embedded (Sharp
Ge et al. 2006) Ge NCs has been reported, and is attributed
to matrix-induced compressive stress on embedded
NCs. The stress could arise due to the volumetric
expansion of Ge during solidification (Wellner et al.
2003), fast growth rate experienced by NCs as a result
of enhanced diffusivity (Choi et al. 2006) and from the
28 30 32 34 36 interface energy. The hydrostatic pressure P in the
Binding Energy (eV) NCs can be estimated as (Cerdeira et al. 1972)
Fig. 3 Ge 3d XPS spectrum of 900 °C annealed sample after ðxstressed  xrelaxed Þ
23 nm of sputter etching P¼ ; ð1Þ
3cx0 ðS11 þ 2S12 Þ
where xstressed, xrelaxed and x0 are the Raman shifts
chemical shift. The chemical shifts found for both of stressed NCs embedded in HfO2, relaxed NCs and
GeO and GeO2 oxide states are consistent with an pure bulk Ge, respectively; c = 0.89 (Choi et al.
oxygen-induced core-level shift per Ge–O bond of 2006) is the mode-Grüneisen parameter, and S11 and
0.8 eV, in agreement with the previously reported S12 are components of the elastic compliance tensor
value (Schmeisser et al. 1986). Ge? and Ge3? states with S11 ? 2S12 = 0.44 9 10-12 dyne-1 cm2 (Choi
are not observed most probably due to instability of et al. 2006). Since no suitable selective etchant for
the sub-oxide phases, favoring the formation of HfO2 is available, the relaxed line position has been
Ge4? and Ge2? states. A relatively high proportion calculated using the phonon confinement model
of GeO2 and GeO in our samples agree with those developed by Richter et al. (Richter et al. 1981).
reported in SiO2-embedded Ge (Das et al. 2007a). According to this model, the first order Raman
The result shows that germanium sub-oxides are spectrum of a NC can be described as a weighted
formed at the interface between Ge NCs and HfO2 contribution of phonon Lorentzians:
matrix in co-sputtered intermediate layer. Z
jCð0; qÞj2
IðxÞ /  2 dq; ð2Þ
Raman spectroscopy ½x  xðqÞ2 þ C20

Quantitative structural analysis can be achieved by where q is the wave vector, x(q) is the phonon
Raman spectroscopy. Figure 4a shows the Raman dispersion curve, C0 is the natural line width of the
spectra of HfO2-embedded Ge NCs in the as-grown corresponding bulk material and C(q) is the Fourier
state and after post growth thermal annealing at 800 coefficient of the weighting function described as
and 900 °C for 30 min in N2 atmosphere. Raman  2 2
2 qL
spectra of NCs are characterized by size-dependent jCð0; qÞj ¼ exp ; ð3Þ
16p2
phonon confinement effects which, for the case of Si
and Ge, are manifested by asymmetric line broadening where L is the NC diameter. An expression for the
and red shift of the peak due to breakdown of the k = 0 average phonon dispersion of Ge within the Brill-
selection rule for Stokes scattering. The scattering ouin zone, x(q), was calculated by Wellner et al.
peak at around 300 cm-1 is attributed to the crystalline (2003), using the Brout sum method and neutron
Ge–Ge phonon vibration mode, indicating the forma- scattering data of Nilsson and Nelin, as (Wellner
tion of Ge NCs. The spectrum exhibits the expected et al. 2003)

123
J Nanopart Res

 1=2 injecting into the charge trapping layer by Fowler–

43565q2r
xðqÞ ¼ x20  ; ð4Þ Nordheim tunneling. The schematic energy band
jqr j þ 0:5766
diagram of the trilayer structure at flatband condition
where qr = (a/2p)q is the reduced wave vector, a is and under the ?ve/-ve gate bias is shown in Fig. 5.
the lattice parameter of bulk Ge, and x0 is the bulk The numerical values of band-gap and band offset are
zone center optical phonon frequency for isotopically taken from the literature (Zhu et al. 2002; Chen et al.
enriched bulk 74Ge. Figure 4b shows the experimen- 2008). Under the ?ve gate bias, electron current from
tal Raman spectrum of 900 °C annealed sample along the Si conduction band is enhanced using high-k
with a simulated spectrum (solid line) calculated HfO2 as a blocking oxide. While in the -ve gate bias,
according to Eq. 2 with Fourier coefficients and the hole injection from the Si valance band can be
phonon dispersion curve given by Eqs. 3 and 4, by enhanced and the electron current from the gate
taking 7 nm as the NCs average diameter. Calculated electrode can be suppressed using high-k HfO2 as a
Raman peak for relaxed Ge (simulated curve) is blocking oxide. To get a high program/erase speed,
found to be 296.3 cm-1 in comparison to the the difference between electron and hole current
experimental value for embedded Ge of 304.6 cm-1 should be higher. It is important to note that the back
(circular symbol). The hydrostatic pressure P calcu- tunneling current can be suppressed using a large
lated using the above values from Eq. 1 is found to be barrier height and high permittivity blocking oxide.
about 2.4 GPa. From the Fig. 4a, it was also observed Therefore, the high-k HfO2 layer not only improves
that the intensity of Ge–Ge phonon peak increases the charge trapping properties but also can improve
after post growth annealing. Although no stress the program/erase speed to facilitate device scaling.
relaxation is observed after either post growth Figure 6 shows the high frequency (100 kHz)
annealing, which is generally observed for silica- C–V curves for 900 and 800 °C annealed sample
embedded Ge NCs (Sharp et al. 2005). Same type of for a sweep voltage of ±5.0 V. An anti-clockwise
results also observed by Sharp et al. (2006) in hysteresis characteristic is observed for both the
sapphire-embedded Ge NCs. It is very important to sample indicating net electron trapping in the Ge
understand stress development in high-k dielectric- NCs-embedded sandwich structure. A small flat-band
embedded germanium nanocrystals as they have voltage shift of 0.12 V is observed for the control
potential for memory device. sample without Ge NCs. However, a large memory
window of 3.4 and 2.1 V are observed for 900 and
Charge injection and trapping in Ge nanocrystals 800 °C annealed sample, respectively, for a voltage
sweep of ±5.0 V. Thus the effect of mobile ions on
Ge nanocrystal trilayer capacitors have been utilized the charge trapping can be neglected. This suggests
to capture the injected carriers from the channel, that the origin of C–V hysteresis can be attributed to
which cause a variation in the threshold voltage of the injected charges mainly in NCs or at the interfaces
memory device. A relatively thicker blocking oxide is between the NCs and the surrounding oxides, rather
useful to prevent the carriers from gate electrode than the traps in HfO2. A maximum flat band voltage

Fig. 4 a Raman spectra of (b)

the trilayer structure in the
as deposited (a) Experimental
o
800 C Simulated
as-grown and annealed
Intensity (arb. units)

Intensity (arb. units)

o
900 C
state. b Raman spectra of
Ge NCs embedded in HfO2
for 900 °C annealed sample
(open circle), and solid line
is the phonon confinement
simulation for the case of
fully relaxed NCs

260 280 300 320 340 260 280 300 320 340
-1
Raman shift (cm-1) Raman shift (cm )

123
 J Nanopart Res

(a)
Vacuum level the thickness and relative permittivity of the control
oxide, respectively, tNC and eNC are the diameter and
4.05 eV 2.87 eV 4.15 eV
relative permittivity of the NC, respectively and e0 is
1.18 eV
the permittivity of the free space.
1.28 eV
Ec
Although C–V measurement has been widely
Ev Ge-
5.8 eV Al studied to obtain device characteristics due to the
p-Si NC ease of experimental setup and data analysis, the
G–V measurement is a relatively sensitive method
and can provide further insights into the electrical
HfO2 HfO2
operation of the devices (Sharp et al. 2005). Recently,
(b) Ge-NC
(c) Ge-NC Huang et al. (2003) and Ng et al. (2006) have
Ec reported energy loss by NCs during G–V measure-
Ev
Al
p-Si
ments. Figure 7a and b shows the C–V and
Gate Al
Gate G–V characteristics of the trilayer MOS capacitor
Ec (900 °C annealed sample) for different sweep volt-
Ev
p-Si HfO2 HfO2 ages. G–V curves show large conductance peak (Gp)
HfO2 shift and a large magnitude during the forward and
HfO2
reverse sweeping. This is explained by the larger gate
Fig. 5 Schematic energy band diagrams of p-Si/HfO2/Ge-NC/ capacitive coupling factor resulting from the higher
HfO2/Al memory structure at a flatband condition, and under dielectric constant HfO2 cap layer. Since a higher
b ?ve and c -ve gate voltage
electric field is channeled to the NCs from the applied
gate bias, this results in more NCs being active in the
o
800 C conduction process (Ng et al. 2006). Conductance
1.0
900 C
o
peak magnitude is also slightly larger for the reverse
Normalized Capacitance

sweep as compared to that for the forward sweep.

0.8 This could possibly be explained by the slightly
larger electric field across the gate structure during
0.6 the reverse sweep. From the C–V plot in Fig. 7a, the
flatband voltage VFB is determined for each sweep
range and compared with the gate voltage value
0.4
(Vpeak), where the conductance peak occurs in the
G–V plot in Fig. 7b. As observed in Fig. 8, VFB tracks
0.2 Vpeak closely, that is the conductance peak occurs
close to flatband voltage and in the depletion bias
-4 -2 0 2 4
regime. This is because at depletion, the minority
Voltage (V)
carrier density at the silicon tunnel dielectric interface
Fig. 6 High-frequency C–V characteristics of MOS capacitor is reduced. As a result, carrier capture rates slow
with Ge nanocrystals in high-k HfO2 matrix for 800 and down and Ge NCs cannot keep pace with the AC gate
900 °C annealed sample
voltage, resulting in an energy loss. Hence, the
shift of 3.4 and 2.1 V obtained for NC-MOS devices energy loss is highest, when the conductance between
give rise to a stored charge density Ncharge of the gate and silicon substrate peaks at a gate bias
7.9 9 1012 and 4.8 9 1012 cm-2, respectively, using close to VFB.
(Hori et al. 1992) For a better understanding of the trapping charac-
teristics, the frequency dependent C–V behavior has
DVFB also been investigated for 900 °C annealed sample.
Ncharge ¼  ; ð5Þ
q tCO
e0 eCO þ etNC
NC
Almost similar anti-clockwise C–V hysteresis in the
frequency range 10 kHz to 10 MHz was observed in
where DVFB is the flatband voltage shift, q is the Fig. 9, which suggests that the hysteresis arises from
magnitude of the electronic charge, tCO and eCO are the same origin. Moreover, there is no stretch-out in

123
J Nanopart Res

Fig. 7 High-frequency 1.4

(-2V,2V)
a C–V and 40 (a) (-2.5V,2.5V)
(b)
b G–V characteristics of 1.2 (-3V,3V)

Conductance ( S)
900 °C annealed sample for

Capacitance (pF)
35 (-4V,4V)
different sweep voltages 1.0 (-5V,5V)
30
(-2V,2V) 0.8
(-2.5V,2.5V)
25 (-3V,3V)
0.6
(-4V,4V)
20 (-5V,5V)
0.4

15 0.2
-4 -2 0 2 4 -4 -3 -2 -1 0 1 2 3 4
Gate Voltage (V) Gate Voltage (V)

2.0 10KHz
50KHz
1.5 1.0 100KHz

Normalized Capacitance
500KHz
1.0 750KHz
VFB or Vpeak (V)

Vpeak(forward) 0.8 1MHz

0.5
Vpeak(reverse) 10MHz
0.0 VFB(forward)
VFB(reverse) 0.6
-0.5

-1.0
0.4
-1.5
2.0 2.5 3.0 3.5 4.0 4.5 5.0 -4 -2 0 2 4
Sweep Voltage (V) Gate Voltage (V)

Fig. 8 Plot of the gate voltage corresponding to the conduc- Fig. 9 Frequency dependent C–V characteristics at room
tance peak (Vpeak) and flatband voltage (VFB) from (C–V plot) temperature for 900 °C annealed sample
versus the gate sweep voltage

is presented in Fig. 10. Ge NCs-embedded MOS

the C–V characteristics along the gate voltage axis for capacitor was initially charged for 5 s at a bias of
the entire experimental frequency range at room -5 V, followed by C–t measurements by changing
temperature. This is consistent with the fact that the the gate voltage to the flat-band value. The discharg-
hysteresis is not due to interface traps, as they ing process is found to be logarithmic with time. The
generally give rise to frequency dependent C–V char- C–t curve consists of two regimes: the first is the
acteristics (Nicollian and Brews 1982). The observed initial fast decay, which may be due to the lateral
frequency dispersion at higher frequencies in the charge loss (Winkler et al. 2002) and the Coulomb
accumulation region agrees well with the character- repulsion between electrons confined in NCs (Kim
istics of HfO2 based MOS capacitors. It is noted that et al. 2003b). The slow decay in the second region is
these C–V curve have slightly different shape (e.g. attributed to the leakage via tunneling barrier (Kim
slightly stretched) compared to those in Fig. 7a. This et al. 2003b). After 3.5 9 103 s, the capacitance
may be due to instrument variation, as we have decay is about 21 and 12% for 800 and 900 °C
performed frequency dependent C–V using a HP annealed sample, respectively. It has been seen that
4294A LCR meter and C–V for different sweep for higher temperature annealed sample, the initial
voltage by Keithley-590 C–V analyzer. fast decay is suppressed due to the complete isolation
In order to investigate the discharging mechanism of Ge NCs (Kim et al. 2003b). To study the device
of charges in Ge NCs, capacitance versus time stability, we have measured the endurance character-
(C–t) measurement has been recorded and the result istics in Fig. 11 with ±5 V sweep voltage. We

123
 J Nanopart Res

110 the presence of Ge NCs along with different oxida-

0
800 C tion states of Ge. The observed Ge phonon peak
100 0
900 C position in Raman spectra is influenced by the
compressive stress and phonon confinement. The
90
Charge storage (%)

calculated stress of about 2.4 GPa originates from a

80 liquid–solid phase transition of Ge during cooling.
Sensitive electrical measurements of C–V and
70 G–V have been utilized to investigate charging and
discharging characteristics in Ge NCs. The observed
60
shift in flatband voltage for C–V and conductance
50
peak in G–V curves has been attributed to electron
trapping in Ge NCs. Experimental data have shown
40 that neither an interface defect nor a deep defect is
0 1000 2000 3000 4000
dominant for the corresponding charging and dis-
Time (s)
charging process. An improved memory retention
Fig. 10 Charge retention characteristics of the trilayer mem- time is observed in Ge NCs annealed under an
ory devices annealed at different temperature optimum condition.

Acknowledgments This work was supported in part by

sponsored research grant from DRDO FIR and DST MBE
3
reverse sweep (+5 V to -5 V) projects. One of the authors (S. Das) acknowledges the Council
forward sweep (-5 V to +5 V) of Scientific and Industrial Research, Government of India, for
2
awarding fellowship to carry out this work.

1
VFB( V )

o
800 C o References
900 C
0 Blauwe J (2002) Nanocrystal nonvolatile memory devices.
IEEE Trans Nanotechnol 1:72–77
Cerdeira F, Buchenauer CJ, Pollack FH, Cardona M (1972)
-1 Stress induced shifts of first-order Raman frequencies of
diamond- and zinc-blende-type semiconductors. Phys Rev
B 5:580–593
-2
0 1 2 3 4 Chen JH, Wang YQ, Yoo WJ, Yeo Y-C, Samudra G, Chan
10 10 10 10 10
DSH, Du AY, Kwong D-L (2005) Nonvolatile flash
Number of cycle memory device using Ge nanocrystals embedded in
HfAlO high-k tunneling and control oxides: device fab-
Fig. 11 Endurance characteristics of the memory devices for
rication and electrical performance. IEEE Trans Electron
both 800 and 900 °C annealed samples
Devices 51:1840–1848
Chen HW, Chiu FC, Liu CH, Chen SY, Huang HS, Juan PC,
observed a slight decrease in the hysteresis after 103 Hwang HL (2008) Interface characterization and current
conduction in HfO2-gated MOS capacitors. Appl Surf Sci
cycles.
254:6112–6115
Choi WK, Chim WK, Heng CL, Teo LW, Ho V, Ng V,
Antoniadis DA, Fitzgerald EA (2002) Observation of
Conclusions memory effect in germanium nanocrystals embedded in
an amorphous silicon oxide matrix of a metal-insulator-
semiconductor structure. Appl Phys Lett 80:2014–2016
We have fabricated a trilayer HfO2/Ge-NCs-embed- Choi WK, Chew HG, Zheng F, Chim WK, Foo YL, Fitzgerald
ded HfO2/HfO2 sandwiched memory structure using EA (2006) Stress development of germanium nanocrystals
rf magnetron sputtering. The formation of spherically in silicon oxide matrix. Appl Phys Lett 89:113126–113128
Compagnoni CM, Ielmini D, Spinelli AS, Lacaita AL, Gerardi
shaped NCs of 4.0–9.0 nm diameter has been
C, Perniola L, Salvo B De, Lombardo S (2003) Program/
observed using TEM microscopy. The probing of erase dynamics and channel conduction in nanocrystal
Ge 3d binding energy in XPS spectrum has indicated memories. IEDM Tech Dig 549–552

123
J Nanopart Res

Das K, NandaGoswami M, Mahapatra R, Kar GS, Dhar A, hysteresis loops in SiO2 films containing Ge nanocrystals
Acharya HN, Maikap S, Lee J-H, Ray SK (2004) Charge produced by ion implantation and annealing. Appl Phys
storage and photoluminescence characteristics of silicon Lett 88:071916–071918
oxide embedded Ge nanocrystal trilayer structures. Appl Pourtois G, Houssa M, Delable A, Conard T, Caymax M,
Phys Lett 84:1386–1388 Meuris M, Heyns MM (2008) Ge 3d core-level shifts at
Das K, Goswami MLN, Dhar A, Mathur BK, Ray SK (2007a) (100)Ge/Ge(Hf)O2 interfaces: a first-principles investi-
Growth of Ge islands and nanocrystals using RF magne- gation. Appl Phys Lett 92:032105–032107
tron sputtering and their characterization. Nanotechnology Renault O, Fourdrinier L, Martinez E, Clavelier L, Leroyer C,
18:175301-1-5 Barrett N, Crotti C (2007) High-resolution photoelectron
Das S, Das K, Singha RK, Dhar A, Ray SK (2007b) Improved spectroscopy of Ge-based HfO2 gate stacks. Appl Phys
charge injection characteristics of Ge nanocrystals Lett 90:052112–052114
embedded in hafnium oxide for floating gate devices. Richter H, Wang ZP, Ley B (1981) The one phonon Raman
Appl Phys Lett 91:233118–233120 spectrum in microcrystalline silicon. Solid State Commun
Hanafi HI, Tiwari S, Khan I (1996) Fast and long retention- 39:625–629
time nano-crystal memory. IEEE Trans Electron Devices Schmeisser D, Schnell RD, Bogen A, Himpsel FJ, Roeger D,
43:1553–1558 Landgren G, Morar J (1986) Surface oxidation states of
Hori T, Ohzone T, Odark Y, Hirase J (1992) A MOSFET with germanium. Surf Sci 172:455–465
Si-implanted gate-SiO2 insulator for nonvolatile memory Sharp ID, Yi DO, Xu Q, Liao CY, Beeman JW, Liliental-Weber
applications. IEEE IEDM Tech Dig 92:469–472 Z, Yu KM, Zakharov DN, Ager JW, Charzan DC, Haller EE
Huang S, Banerjee S, Tung RT, Oda S (2003) Electron trap- (2005) Mechanism of stress relaxation in Ge nanocrystals
ping, storing, and emission in nanocrystalline Si dots by embedded in SiO2. Appl Phys Lett 86:063107-1-3
capacitance-voltage and conductance-voltage measure- Sharp ID, Xu Q, Yi DO, Yuan CW, Beeman JW, Yu KM, Ager
ments. J Appl Phys 93:576–581 JW, Chrzan DC, Haller EE (2006) Structural properties of
Kim DW, Kim T, Banerjee SK (2003a) Memory character- Ge nanocrystals embedded in sapphire. J Appl Phys 100:
ization of SiGe quantum dot flash memories with HfO2 114317-1-7
and SiO2 tunneling dielectrics. IEEE Trans Electron Tan Z, Samanta SK, Yoo WJ, Lee S (2005) Self-assembly of
Devices 50:1823–1829 Ni nanocrystals on HfO2 and N-assisted Ni confinement
Kim JK, Cheong HJ, Kim Y, Yi JY, Park HJ (2003b) Rapid- for nonvolatile memory application. Appl Phys Lett 86:
thermal-annealing effect on lateral charge loss in metal- 013107–013109
oxide-semiconductor capacitors with Ge nanocrystals. Wang C–C, Chiou Y–K, Chang C–H, Tseng J–Y, Wu L–J,
Appl Phys Lett 82:2527–2529 Chen C–Y, Wu T–B (2007) Memory characteristics of Au
Lee SJ, Luan HF, Bai WP, Lee CH, Jeon TS, Senzaki Y, nanocrystals embedded in metal-oxide-semiconductor
Roberts D, Kwong DL (2000) High-quality ultrathin CVD structure by using atomic-layer-deposited Al2O3 as con-
HfO2 gate stack with poly-Si gate electrode. IEDM Tech trol oxide. J Phys D 40:1673–1678
Dig 31–34 Wellner A, Paillard V, Bonafos C, Coffin H, Claverie A,
Molle A, Bhulyan Md NK, Tallarida G, Fanclulli M (2006) In Schmidt B, Heinig KH (2003) Stress measurement of
situ chemical and structural investigations of the oxidation germanium nanocrystals embedded in silicon oxide.
of Ge(001) substrates by atomic oxygen. Appl Phys Lett J Appl Phys 94:5639–5642
89:083504–083506 Winkler O, Merget F, Heuser M, Hadam B, Baus M, Spangen-
Ng TH, Chim WK, Choi WK (2006) Conductance-voltage berg B, Kurz H (2002) Concept of floating-dot memory
measurements on germanium nanocrystals memory transistors on silicon-on-insulator substrate. Microelectron
structures and effect of gate electric field coupling. Appl Eng 61:497–503
Phys Lett 88:113112–113114 Zhu WJ, Ma T-P, Tamagawa T, Kim J, Di Y (2002) Current
Nicollian EH, Brews JR (1982) MOS physics and technology. transport in metal/hafnium oxide/silicon structure. IEEE
Wiley, New York Electron Device Lett 23:97–99
Park CJ, Cho KH, Yang W-C, Cho HY, Choi S-H, Elliman RG,
Han JH, Kim C (2006) Large capacitance-voltage

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