Microstructural, Chemical Bonding, Stress Development and Charge Storage Characteristics of Ge Nanocrystals..
Microstructural, Chemical Bonding, Stress Development and Charge Storage Characteristics of Ge Nanocrystals..
Microstructural, Chemical Bonding, Stress Development and Charge Storage Characteristics of Ge Nanocrystals..
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RESEARCH PAPER
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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
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
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Fig. 1 Cross-sectional
TEM micrograph of Ge
NCs embedded in HfO2 for
a 800 °C and b 900 °C
annealed sample
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J Nanopart Res
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)
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J Nanopart Res
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 )
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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
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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)
-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
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J Nanopart Res
1
VFB( V )
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800 C o References
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