JOURNAL OF APPLIED PHYSICS 110, 074505 (2011)

A solution processed nonvolatile resistive memory device with Ti/CdSe

quantum dot/Ti-TiOx/CdSe quantum dot/indium tin-oxide structure
V. Kannan and J. K. Rheea)
Millimeter-Wave INnovation Technology Research Center (MINT), Dongguk University, Seoul 100-715,
Republic of Korea
(Received 22 June 2011; accepted 24 August 2011; published online 4 October 2011)
We report a Ti-TiOx/quantum dot based bipolar nonvolatile resistive memory device. The device
has ON/OFF ratio 100 and is reproducible. The memory device showed good retention
characteristics under stress and excellent stability even after 100 000 cycles of switching operation.
The memory devices are solution processed at room temperature in ambient atmosphere. The
operating mechanism is discussed based on charge trapping in quantum dots resulting in Coulomb
blockade effect with the metal-oxide layer acting as the barrier to confine the trapped charges. The
mechanism is supported by negative differential resistance (NDR) observed exclusively in the ON
C 2011 American Institute of Physics. [doi:10.1063/1.3644973]
state. V

INTRODUCTION terest are fabricated with middle Ti layer thicknesses of 3 nm,

In the past decade, resistive random access memory
(ReRAM) devices are considered as a potential substitute for
FET based flash memory.1–5 Nanoparticles and quantum
dots are of interest due to their potential application in next
generation logic devices.6,7 Quantum dots owing to their
nanometer size scale exhibit quantum confinement effects
that play a dominant role in their electronic properties. Indi-
vidual CdSe quantum dots have discrete energy levels sepa-
rated by 100 meV and charging energies, 150 meV.8–10
These quantum dots surrounded by suitable tunnel barriers
have been studied for their ability to store charges resulting
in memory effects. Memory devices consisting exclusively
of quantum dots are of interest due to their fast switching
capabilities and nano-scale devices.11 Quantum dots embed-
ded in a partially oxidized thin aluminum layer exhibited
bipolar bistable non-volatile memory characteristics with
excellent ON/OFF ratio and fast switching times.12 How-
ever, the actual switching mechanism and memory devices
with other metals with their partially oxide form is particu-
larly interesting. In this paper, we report the observation of
non-volatile memory characteristics with a new structure: Ti/
CdSe quantum dot/Ti-TiOx/CdSe quantum dot/indium tin-
oxide (ITO) and discuss the relevant mechanism based Cou-
lomb blockade in quantum dots.
EXPERIMENTAL
The resistive memory devices with Ti/quantum dot/
Ti/quantum dot/ITO structure were prepared by the spin-
casting method. CdSe quantum dots of size 3.3 nm dis-
persed in toluene procured from Sigma-Aldrich were
employed in the device fabrication. First CdSe quantum dots
are spin-casted on a pre-cleaned indium tin-oxide (ITO)
coated glass substrate at 3 000 RPM. Subsequently, the sam-
ples are well dried at 120  C for 10 min. Three samples of in-
a)
Author to whom correspondence should be addressed. Electronic mail:
jkrhee@dongguk.edu.
5 nm, and 7 nm. A titanium layer is deposited by e-beam
evaporation with chamber pressure of 1  106 Torr. After
deposition of the middle Ti layer, the sample is kept in open
air for at least 1 h so that the exposed Ti surface can form a
thin layer of titanium oxide. This is followed by another layer
of CdSe quantum dots by spin-casting. The thickness of the
all CdSe quantum dot layer is approximately 50 nm. Finally,
top contact is made from the e-beam deposited 100 nm thick
Ti layer with diameter of shadow mask ranging from 1 mm to
30 lm, while the bottom contact is taken from ITO. The film
thicknesses were measured using Alpha-step surface profiler.
The current-voltage (I-V) characteristics were carried out using
“Keithly 4200DC parameter analyzer” at room temperature.
RESULTS AND DISCUSSION
A standard reference device with Ti/quantum dot/ITO
was prepared (without the middle Ti layer). This reference
device did not show any switching characteristics. Figure 1
shows the switching characteristics of the resistive memory
devices with two stable conducting states. Initially, the device
was in high conducting state (ON). At a forward sweep volt-
age of around 1.52 V, the device switched to low conduct-
ing state (OFF). The device could be turned ON by applying
a negative sweep voltage of around 1 V. Both states were
stable and remained in the state even after removal of the
bias. Thus non-volatile bistable resistive memory is demon-
strated. The ON/OFF ratio is around 100. Several devices
(>12 numbers) showed switching characteristics consistent
with the Fig. 1. The switching process was repeatable; the en-
durance test was done with pulse generator in “burst mode.”
The device was stable even after 105 cycles of switching
operation as shown in Fig. 2. Figure 3 shows the retention
test carried out in both ON and OFF states with a constant
bias voltage of 0.2 V for 104 s at room temperature (RT) as
well as retention test at 150  C for 1 h. The device exhibits
good stability with minimal change in ON/OFF resistances
under stress. Devices fabricated with a simpler structure with

0021-8979/2011/110(7)/074505/4/$30.00 110, 074505-1 C 2011 American Institute of Physics

V
074505-2 V. Kannan and J. K. Rhee
FIG. 1. (Color online) I-V characteristics of the ITO/CdSe quantum dot/Ti-
TiOx/CdSe quantum dot/Ti resistive memory device for three middle Ti
layer thicknesses of 3 nm, 5 nm, and 7 nm.
Ti/Ti-TiOx/CdSe quantum dot/ITO also showed two conduct-
ing states but had reliability issues. This could be to the high
roughness value of the ITO substrate (root mean square 8
nm from atomic force microscopy analysis).
The ON/OFF switching mechanism can be described
based on charge trapping in CdSe quantum dots. A memory
device with aluminum in place of titanium was previously
reported by us with mechanism based on charge trapping/de-
trapping in quantum dots.12 The thin titanium middle layer
when exposed to open atmosphere will form an oxide layer
consisting of Ti/TiOx. Figure 4 shows the scanning electron
micrograph of the middle Ti layer confirming the presence
of nano-particle/clusters. Energy dispersive x-ray spectra
(EDS) of this layer reveal the presence of oxygen. Here the
TiOx is believed to play major role in charge trapping and
leading to OFF state. The charge trapping and subsequent
blocking of further electrons entering the quantum dot could
be described on the basis of Coulomb blockade effect. In
other words, as illustrated in Fig. 5, if the quantum dot is
charged with an electron, the tunneling path through it will
be effectively shut off by the large Coulomb charging
energy. The total tunneling current through the structure is
FIG. 2. Endurance data obtained for ITO/CdSe quantum dot/Ti-TiOx/CdSe
quantum dot/Ti device with middle Ti layer thickness of 5 nm.
J. Appl. Phys. 110, 074505 (2011)
FIG. 3. (Color online) Retention test results for the device for 10 000 s at
RT and 1 h at 150  C at a constant 0.2 V bias.
thus determined by the overall charging state of the individ-
ual CdSe quantum dots.13,14 Moreover, there was marginal
variation in I-V characteristics of the device even at 200  C
as shown in Fig. 6. TiOx acts as the barrier for trapped
charges in the quantum dot. Therefore, the net content of
TiOx present in the middle layer can be expected to play a
significant role in the amount of electrons trapped.
A close examination of the I-V plot shown in Fig. 7 with
a linear scale in both axes reveals some interesting features,
particularly in the forward sweep. The first conduction path
from 0 to 1.1 V is nearly linear. The second conduction path
from 1.1 to 1.2 V exhibits a steep decrease in current indicat-
ing negative differential resistance (NDR). The peak-to-val-
ley ratio is around 1.6. In the third conduction path from 1.2
to 1.5 V, a near linear increment of current with voltage can
be observed. The actual switching of device from ON to
OFF state occurs around 1.8 V with an abrupt reduction in
the injection current. A subsequent scan shows, as expected,
the device in the OFF state. More importantly, the NDR phe-
nomenon is not observed in the OFF state. Similarly, I-V
characteristics were observed in many such devices. Figure 8
shows the I-V characteristics (in log scale) of both ON and
FIG. 4. Scanning electron micrograph of the middle Ti layer showing the
presence of nano-particle/cluster.
074505-3 V. Kannan and J. K. Rhee
FIG. 5. (Color online) Illustration for the ON/OFF states based on Coulomb
blockade in CdSe quantum dot/TiOx structure.
OFF states for V < Turn off voltage. In the region the ON
state follow a power law, i.e., I ¼ AVn, where n is the expo-
nent factor (n ¼ 1 for perfect ohmic conduction) and A is the
coefficient that depends on the resistance state.15 As shown
in Fig. 8, n is close to 1 for ON state, whereas in the OFF
state, the curve is slightly exponential with n > 1, indicating
that the ON state conduction is ohmic in nature, while the
OFF state appears to include more complex transport mecha-
nisms. The ON state ohmic conduction could be explained
on the basis of tunneling of electrons through the quantum
dot/TiOx structure. The OFF state conduction with a mar-
ginal exponential behavior could partly be due to tunneling
emission current,16 but the problem demands a more detailed
study.
J. Appl. Phys. 110, 074505 (2011)
FIG. 6. I-V plot of the resistive memory device at 200  C.
The observed NDR exclusively in the ON state is dis-
cussed based on the theory adopted for a double barrier res-
onant tunneling diode (DBRTD) and Coulomb blockade
effect. Metal-oxide is considered as the barrier and the
CdSe quantum dot as the well. Further, we find that
the results corroborate with the proposed mechanism for
the observed memory characteristics. In a quantum dot, the
energy levels are not continuous but discrete giving rise to
quasi-bound states. When one of these quasi-bound states in
the conduction band of the CdSe quantum dot line up with
the Fermi level of the left contact, resonance occurs giving
rise to increase in current. As the voltage is further
increased, the resonance condition is not satisfied; this leads
to sharp reduction in current value exhibiting NDR phe-
nomena. Such NDR characteristics have been recently
reported in polymer/quantum dot based nanocomposite
devices.17–19
FIG. 7. (Color online) I-V plot in linear
scale exhibiting NDR exclusively in
ON state.
074505-4 V. Kannan and J. K. Rhee J. Appl. Phys. 110, 074505 (2011)

does not require a “filament forming” high-voltage and

expected to be in the OFF state initially.20
In summary, a quantum dot based nonvolatile resistive
memory device is demonstrated with ON/OFF ratio of 100.
The retention and endurance test show good stability and
reliability. The operating mechanism is proposed based on
Coulomb blockade with charge trapping/de-trapping in quan-
tum dots with metal-oxide layer serving as barrier. The
memory devices are easy to fabricate, ultra-thin, and solution
processed and have a low cost, promising to be one the
potential candidates for the future memory applications.

ACKNOWLEDGMENTS
This work was supported by the Millimeter-wave INno-
vation Technology Research Center (MINT), Dongguk Uni-
FIG. 8. (Color online) Plot of log I vs log V for V< turn off voltage for versity, Republic of Korea.
both ON and OFF states.
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