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Organic Memory

High-Performance Flexible Organic Nano-Floating

Gate Memory Devices Functionalized with Cobalt
Ferrite Nanoparticles
Ji Hyung Jung, Sunghwan Kim, Hyeonjung Kim, Jongnam Park,* and Joon Hak Oh*

Nano-floating

gate memory (NFGM) devices are transistor-type memory devices

that use nanostructured materials as charge trap sites. They have recently attracted
a great deal of attention due to their excellent performance, capability for multilevel
programming, and suitability as platforms for integrated circuits. Herein, novel
NFGM devices have been fabricated using semiconducting cobalt ferrite (CoFe2O4)
nanoparticles (NPs) as charge trap sites and pentacene as a p-type semiconductor.
Monodisperse CoFe2O4 NPs with different diameters have been synthesized by
thermal decomposition and embedded in NFGM devices. The particle size effects
on the memory performance have been investigated in terms of energy levels and
particleparticle interactions. CoFe2O4 NP-based memory devices exhibit a large
memory window (73.84 V), a high read current on/off ratio (read Ion/Ioff) of
2.98 103, and excellent data retention. Fast switching behaviors are observed due
to the exceptional charge trapping/release capability of CoFe2O4 NPs surrounded by
the oleate layer, which acts as an alternative tunneling dielectric layer and simplifies
the device fabrication process. Furthermore, the NFGM devices show excellent
thermal stability, and flexible memory devices fabricated on plastic substrates exhibit
remarkable mechanical and electrical stability. This study demonstrates a viable
means of fabricating highly flexible, high-performance organic memory devices.

1. Introduction
Conventional flash memory devices based on inorganic materials are typically produced on a limited number of rigid
J. H. Jung, Prof. J. H. Oh
Department of Chemical Engineering
Pohang University of Science and
Technology (POSTECH)
Pohang, Gyeongbuk 790-784, Korea
E-mail: joonhoh@postech.ac.kr
S. Kim, H. Kim, Prof. J. Park
School of Energy and Chemical Engineering
Ulsan National Institute of Science
and Technology (UNIST)
Ulsan 689-798, Korea
E-mail: jnpark@unist.ac.kr
DOI: 10.1002/smll.201501382
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DOI: 10.1002/smll.201501382

substrates using expensive fabrication processes that require

high temperatures and vacuum conditions. However, there is
currently increasing demand for flexible memory elements
that can be manufactured using low-cost processes on flexible or stretchable substrates. In this regard, organic memory
devices, which are inexpensive to fabricate, lightweight, and
amenable to flexible plastic substrates, have attracted a great
deal of attention.[18] To realize flexible flash memory devices,
extensive efforts have been made to optimize memory performance using various floating gate materials, such as
polymer electrets,[9,10] organic semiconductors,[5,11] and nanostructured materials.[1214] Electrically bistable behaviors
can be observed in floating gate memory devices, with the
conductivity at a given gatesource bias voltage dependent
on the previous operation.[15] Charge carriers induced at
the semiconductordielectric interface by an external gate
voltage can be trapped into floating gates during a program
operation and released during an erase operation, resulting

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shift.[16]

in a threshold voltage
This shift is referred to as a
memory window or hysteresis.
Among the various flash memory devices, nano-floating
gate memory (NFGM) devices employing nanostructured
materials as the floating gates are particularly promising as
next-generation memory devices due to their high speed of
operation, outstanding reliability, capability of multilevel
programming, and suitability as platforms for integrated
circuits.[1719] In particular, the electrical properties of an
NFGM device can be easily controlled by modulating the
energy levels of the embedded nanostructured materials, via
the manipulation of their size and shape. Most studies on
organic NFGM devices performed to date employed metallic
nanoparticles (NPs).[15,2023] Au NPs have been used extensively in NFGM devices because of their high work function
and chemical stability.[22] Thermal evaporation is commonly
used to deposit metallic NPs. This method, however, requires
high-vacuum conditions and does not allow for controlling the size, shape, and density of NPs because of Ostwald
ripening, in which small NPs tend to dissolve and redeposit
onto larger NPs during evaporation.[24] On the other hand,
semiconducting or metal oxide NPs are far less common in
memory devices despite their cost-effective production, due
to their relatively low electrical memory performance.[2529]
Here, we report the fabrication of high-performance
organic NFGM devices based on pentacene and cobalt ferrite
(CoFe2O4) NPs as the semiconducting layer and charge trapping sites, respectively. Pentacene was chosen as the active
layer as it is a model compound for p-channel organic semiconductors. CoFe2O4 NPs were applied to organic NFGM
devices due to their relatively higher electrical conductivity,
excellent chemical stability, and mechanical strength compared with other metal oxide NPs.[3032] In addition, they
are highly suitable for the low-cost fabrication of NFGM
devices compared with conventional metallic NPs. These
unique properties have led to the use of CoFe2O4 NPs in
various applications, including ionic fluids,[33] sensors,[34] data
storage,[35] and bioapplications, such as drug delivery systems
for biological labeling or magnetic hyperthermia.[36] Accordingly, many approaches to the synthesis of CoFe2O4 NPs have
included alkalide reduction,[37] reverse micelles,[38,39] and
coprecipitation.[40] However, synthesized CoFe2O4 NPs often
suffer from broad size distributions and particle aggregation.
In this study, monodisperse semiconducting CoFe2O4 NPs
were synthesized and employed in organic NFGM devices for
the first time. The CoFe2O4 NPs were synthesized by thermal
decomposition of an inexpensive and nontoxic metaloleate
complex precursor.[4143] From the viewpoint of synthetic
methodologies for metal oxide NPs, although several methods
for synthesizing CoFe2O4 NPs have been reported,[41,42] synthesis of uniform NPs with several nanometer diameters in
high yield and good reproducibility has been challenging.
We successfully fabricated size-tunable and monodisperse
CoFe2O4 NPs with the diameter of 5, 8, and 11 nm by controlling the primary nucleation time via simply adjusting Ar
bubbling rate.[44] These solution-processed CoFe2O4 NPs
enabled simple, cost-effective, fast, and density-controllable
deposition onto target substrates at room temperature via a
spin-casting technique. In addition, a self-assembled oleate

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layer surrounding the NPs acted as a tunneling dielectric layer. This reduced the number of fabrication steps and
enhanced the data retention properties of the memory device.
The resulting NFGM devices exhibited outstanding memory
performance, including a large memory window, fast and
reversible switching behavior, high read current on/off ratio
(read Ion/Ioff), and good data retention. These properties are
comparable to those of high-performance organic NFGM
devices based on expensive Au NPs. The excellent memory
performance of these CoFe2O4 NP-embedded NFGM devices
resulted from the exceptional charge trapping and release
capability of CoFe2O4 NPs.

2. Results and Discussion

2.1. Electrical Memory Characteristics of NFGM Devices
CoFe2O4 NPs with diameters of 5, 8, and 11 nm were synthesized from a low-cost and nontoxic (Co2+Fe23+)oleate
precursor complex through a modification of the previously
reported thermal decomposition method.[43] The details
about the synthetic procedures of CoFe2O4 NPs are described
in Experimental Section. Transmission electron microscopy
(TEM) images of the resulting monodisperse CoFe2O4 NPs
are shown in Figure 1. The physical characteristics of the
CoFe2O4 NPs were calculated from 50 randomly chosen
particles in the TEM images. The three different sized NPs
showed narrow size distributions of 5.59 0.65 (size variation
10%), 8.05 0.57 (size variation 7%), and 11.30 0.76 nm
(size variation 5%) (Figure S1, Supporting Information).
Although various ferrite NPs have been synthesized, only
few experimental results on the synthesis of iron oxide NPs
smaller than 5 nm have been reported due to the large size
distribution of ultrasmall ferrite NPs.[39,44,45] The diameter
of the CoFe2O4 NPs could be controlled by varying the Ar
bubbling rate in the reacting solution, which can strongly
affect the nucleation stage by absorbing the heat generated
from exothermic multiple-bonds formation reactions in the
nucleation step.[46] The resulting monodisperse NPs were
synthesized through the separation of nucleation and growth
step in the heating-up process. A solution of CoFe2O4 NPs
(2 mg mL1) was prepared in n-hexane and spin-coated onto
n-octadecyltrimethoxysilane (OTS)-modified Si/SiO2 wafers.
A pentacene layer (50 nm) was then thermally deposited
onto the CoFe2O4 NP-coated substrates. Gold sourcedrain
electrodes (40 nm) were subsequently thermally deposited
onto the pentacene layer using shadow masks. Figure 2 shows
a schematic illustration of the CoFe2O4 NP-based NFGM
device structure with cross-sectional bright-field (BF), highangle annular dark-field (HAADF) scanning transmission
electron microscopy (STEM, left inset), and TEM images
(right inset) of the 8 nm CoFe2O4 NPs.
The transfer characteristics of NFGM devices based on 5,
8, and 11 nm CoFe2O4 NPs are presented in Figure 3. The
electrical memory characteristics are summarized in Table
1. Compared with a small memory window (7.60 V) of typical organic thin-film transistors (OTFTs), all of the transfer
curves of the NFGM devices based on CoFe2O4 NPs exhibited

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a)

2 0

b)

n m

c)

2 0

d)

n m

e)

2 0

f)

n m

Figure 1. TEM images of CoFe2O4 NPs with diameters of a,b) 5, c,d) 8, and e,f) 11 nm.

much larger memory window (>62 V). The NFGM devices

also exhibited a counterclockwise hysteresis loop, indicating
p-type behavior, due to the trapping and release of charge
carriers by the NPs. After functionalization with CoFe2O4
NPs, the average read Ion/Ioff increased from 0.621 to >103
with a sweep of the gate voltage between 60 and +60 V.
Although it is difficult to compare the electrical characteristics of memory devices with those of other devices composed of different materials, the memory performance of
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8 nm CoFe2O4 NP-embedded NFGM devices (a large

memory window of 73.84 V and high read Ion/Ioff of
2.98 103) is comparable to those of the best-performing
organic NFGM devices based on Au NPs.[20] However, the
charge carrier mobility of the memory devices was decreased
after the integration of NPs, most likely due to the more
disturbed molecular packing by underlying NPs (Figure S2,
Supporting Information). It is also common to observe
such mobility degradation in organic NFGM devices as

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electric field from the lowest unoccupied

molecular orbital (LUMO) of pentacene
to the conduction band of CoFe2O4 NPs
by passing through the thin oleate layer
(2 nm). As a result, negatively charged
NPs generated by the accumulation of
electrons can induce a negative internal
electric field. This leads to accumulation of
holes in the channel region and a positive
threshold voltage shift, which maintains a
high conductance state during the subsequent read on operation (at VGS = 0 V).
Conversely, during an erase operation (at
VGS = 60 V), a negative threshold voltage
shift is induced by the release of electrons
Figure 2. A schematic configuration of the NFGM devices based on CoFe2O4 NPs with cross- from the NPs or by recombination with
sectional bright-field (BF) and high-angle annular dark field (HAADF) scanning transmission holes transported by the strong negative
electron microscopy (STEM) images (left inset), and a TEM image of 8 nm CoFe2O4 NPs external electric field, which results in a
(right inset).
low conductance state during the read off
operation (at VGS = 0 V).
considerable charge carriers forming drain current in the
Although the charge carriers that contribute directly to
active layer can be trapped in nano-floating gates.[15]
the drain current of p-type pentacene active layer are holes,
The energy levels of the NPs were estimated from cyclic the floating gate architecture allows trapped negative charge
voltammograms (CVs) and UVvis absorption spectra. These carriers (electrons) to also affect output current. In addidata provided a means of determining the charge trapping tion, the energy barrier for electron transport between the
and release mechanism of the NFGM devices and effects of LUMO of pentacene and the conduction band of CoFe2O4
NP size on the electrical memory characteristics. The energy NP is lower than that for hole transport between the highest
level of the valence band of CoFe2O4 NP was obtained from occupied molecular orbital (HOMO) of pentacene and the
the cyclic voltammetric data shown in Figure S3 (Supporting valence band of CoFe2O4 NPs.
As summarized in Table 1, the memory window
Information). The energy bandgap was determined from a
plot of the modified KubelkaMunk function as a function of (73.84 6.34 V) of NFGM devices based on 8 nm CoFe2O4
the energy of exciting light derived from the UVvis absorp- NPs was slightly larger than that of 5 nm NP-based ones
tion spectra (Figure S4, Supporting Information).[47] The (68.27 2.77 V). NFGM devices based on 11 nm CoFe2O4
energy band diagrams of pentacene[48,49] and the various sizes NPs had the smallest memory window of 62.51 7.16 V,
of CoFe2O4 NPs are shown in Figure 4a. The energy levels although they were expected to exhibit the largest memory
of CoFe2O4 NPs derived from electrochemical/photochem- window based on their relative energy levels compared to
ical measurements are summarized in Table S1 (Supporting those of the 5 or 8 nm CoFe2O4 NPs. This is most likely due to
Information). As the diameter of the NPs increased from 5 to the formation of irregular aggregates of 11 nm CoFe2O4 NPs.
11 nm, the energy level of the valence band increased gradu- Atomic force microscopy (AFM) phase images indicated that
ally from 6.56 to 6.52 eV, while that of the conduction band 5 and 8 nm CoFe2O4 NPs on Si/SiO2 wafers (Figure S5, Supdecreased from 3.80 to 3.94 eV. Concurrently, the energy porting Information) were relatively uniformly dispersed.
bandgap decreased from 2.76 to 2.58 eV. Schematic energy In contrast, the 11 nm CoFe2O4 NPs formed close-packed
band diagrams for program/erase (P/E) operations and charge aggregates. This aggregation was confirmed on TEM images
trapping/release mechanisms are shown in Figure 4b. During a (Figure 1e,f). This aggregation likely prevents the uniform
program operation (at VGS = 60 V), electrons at the semicon- deposition of pentacene during thermal evaporation, thereby
ductordielectric interface can be transferred by the strong hindering charge trapping and release, resulting in a smaller

-6

10

-7

10

-8

10

-9

10

-10

10

-11

-5
b) 10

-60 -40 -20 0 20 40 60

VGS (V)

10

-6

10

-7

10

-8

10

-9

10

-10

10

-11

erase
program

c) 10-5

-ID (A)

10

erase
program

-ID (A)

-ID (A)

-5
a) 10

-60 -40 -20 0 20 40 60

10

-6

10

-7

10

-8

10

-9

10

-10

10

-11

VGS (V)

erase
program

-60 -40 -20 0 20 40 60

VGS (V)

Figure 3. Transfer curves of the NFGM devices based on a) 5, b) 8, and c) 11 nm CoFe2O4 NPs at VDS = 30 V.

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Table 1. Electrical memory characteristics of the NFGM devices based on CoFe2O4 NPs in various sizes and pentacene-based OTFTs.
avg, initial
[cm2 V1 s1]

max, initial
[cm2 V1 s1]

Vt, initial
[V]

Vt, program
[V]

Vt, erase
[V]

Vt
[V]

Read Ion
[A]

Read Ioff
[A]

Read Ion/Ioff

2.33 103
(1.95 103)

2.61 103
(1.92 103)

4.53
(8.13)

32.46
(1.78)

35.82
(2.09)

68.27
(2.77)

8.60 107
(7.52 107)

1.64 1010
(3.06 1011)

5.13 103
(3.86 103)

1.96 103
(6.81 104)

2.24 103
(8.44 104)

3.38
(5.39)

31.63
(4.25)

42.21
(3.48)

73.84
(6.34)

5.97 107
(4.08 107)

2.28 1010
(1.07 1010)

2.98 103
(5.29 102)

11

1.04 103
(3.05 104)

1.18 103
(2.56 104)

6.18
(3.65)

30.52
(3.16)

31.99
(4.05)

62.51
(7.16)

4.49 107
(1.61 107)

3.27 1010
(8.87 1011)

1.35 103
(1.99 102)

No NPs

5.17 101
(1.12 101)

5.21 101
(1.11 101)

20.75
(4.67)

24.91
(2.05)

32.51
(2.26)

7.60
(1.13)

1.32 1010
(1.12 1011)

2.25 1010
(7.48 1011)

6.21 101
(1.24 101)

Size of NPs
[nm]

memory window and decreased charge mobility. The aggregation of 11 nm CoFe2O4 NPs may be attributed to the stronger
coercivity and van der Waals interactions among the larger
NPs.[50,51] It has been experimentally verified that van der
Waals forces increase with the size of CoFe2O4 NPs because
of permanent dipole moments in their spinel structures.[52]
The inverse spinel structure of CoFe2O4 NPs was confirmed
in X-ray patterns (Figure S6, Supporting Information, XRD).
Among the devices tested, the best electrical memory
performance was observed from NFGM devices based on
8 nm CoFe2O4 NPs. Therefore, these devices were selected
for further characterization. The typical output curves of
8 nm CoFe2O4 NP-embedded NFGM devices are shown in
Figure 5a. The drain current (ID) responses for the repeated
pulse bias of P/E operations were investigated to measure
memory switching speed and electrical stability (Figure 5b).

Gate voltages of 60, 0, 60, and 0 V were sequentially and

repeatedly applied for program, read on, erase, read off operation, respectively. This switching cycle is usually called as
write-read-erase-read (WRER) cycle. As shown in Figure 5b,c,
fast and stable switching ID responses with the value of read
Ion/Ioff above 103 was maintained over 1000 WRER cycles.
In addition, data storage capability estimated from data
retention test is one of the important factors in nonvolatile
memory devices. A read Ion/Ioff (at VGS = 0 V) of 1.62 103
was maintained over 1000 s as well (Figure 5d).
To investigate the effects of P/E operation bias voltages on memory performance, the gatesource voltage was
gradually increased from 10 to 60 V at intervals of 10 V, as
shown in Figure S7 (Supporting Information). The results are
summarized in Table S2 (Supporting Information). Both the
memory window and read Ion/Ioff remained low and constant
from 10 to 30 V, but started to increase above 30 V. These
observations indicated that the CoFe2O4 NPs start to behave
as charge trap sites above 30 V. The memory window and
read Ion/Ioff of these devices increased to 76.79 V and
2.72 103, respectively, at 60 V.
The following equation can be used to estimate the
charge carrier storage capacity of 8 nm CoFe2O4 NPs:[53]
n =

Figure 4. a) Energy band diagrams of pentacene and CoFe2O4 NPs

in different sizes and b) a schematic energy band diagrams during
program (left) and erase operations (right) for the charge trapping/
release mechanism description.
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Vt C i
e

(1)

where n is the amount of transferred charge carriers, Ci

is the capacitance of the blocking dielectric layer, and e is
the elementary charge. Equation (1) indicates that ca. 1.57
1013 charge carriers are expected to be transferred. The
deposition density of the 8 nm CoFe2O4 NPs in the NFGM
devices is 8.29 1011 cm2 based on AFM phase images
of NPs on OTS-treated Si/SiO2 wafers. These data indicate
that approximately 18 charge carriers were trapped in each
CoFe2O4 NP. It is noteworthy that the charge trapping capability of the CoFe2O4 NPs is comparable to that of Au NPs
without the aid of additional tunneling dielectric or selfassembled monolayer (SAM) treatments on the dielectric
layer.[6,20,24]
The thermal stability of the memory devices has also been
investigated for the practical application in electronic appliances. The NFGM devices showed thermally and electrically
stable behaviors in repeating P/E cycles and data retention
test at 100 C (Figure S8, Supporting Information). In addition, it is notable that not only charge carrier mobility but
also ID increases as the temperature of the memory device

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due to the insulating nature of hydrocarbon chains.[15] In conventional NFGM

60
10
0.5
50
50
devices, a tunneling dielectric layer is usu40
-3
10
0
0.4
ally prepared at high temperatures and
30
20
-5
-50
under high vacuum over a long period.
10
10
I
0.3
on
read off
erase
0
-100
This step is considered vital for charge car-7
10
0.2
rier storage in NPs, which is required for
-150
-9
10
data retention. In addition, optimization of
-200
0.1
Ioff
-11
the thickness of the tunneling layer, which
-250
10
0.0
100
150
200
250
300
separates charge trap sites from the semi-60 -50 -40 -30 -20 -10 0
Time (s)
conducting layer, is important to achieve
VDS (V)
a balance between data retention and
P/E speed.[22] A thick tunneling dielectric
c) 10-6
d) 10-6
layer
can degrade P/E speed and increase
-7
10
-7
power consumption.[18] Conversely, a thin
10
-8
layer can enhance the P/E operation speed
10
programmed state
-8
programmed state
10
but an excessively thin layer can limit
-9
10
the number of P/E cycles and/or result
-9
10
erased state
-10
in charge loss or leakage current through
erased state
10
defects in the layer.[61]
-10
-11
10
10
To verify the effects of an additional
0 200 400 600 800 1000
0 200 400 600 800 1000
tunneling dielectric layer in our memory
Time (s)
P/E cycles
devices, 10 nm thick Al2O3 thin film was
Figure 5. Electrical memory characteristics of programmable 8 nm CoFe2O4 NP-based NFGM deposited by atomic layer deposition (ALD)
devices: a) Output curves, b) drain current response for P/E cycles, c) electrical endurance for
between the CoFe2O4 NPs and the penta1000 P/E repeating cycles, and d) data retention test.
cene layer. Al2O3 is widely used as an insulator in various electronic devices because of
rises, which can be attributable to the facilitated charge hop- its high electrical breakdown field, high dielectric constant, and
ping.[54] The mechanism can be expressed as:[5558]
large bandgap.[62] In addition, ALD methods have simple and
accurate thickness control, resulting in dense and pinhole-free
thin films with excellent thickness uniformity over large areas.[63]

qa mV q t
I D = Sqa m ne v f exp

(2)

2
dkT
kT
The electrical memory characteristics of 8 nm CoFe2O4

NP-based NFGM devices with and without the Al2O3 tunwhere S is the contact area, d is assumed to be the film thick- neling dielectric layer are summarized in Table S3 (Supporting
ness, q is the electronic charge, V is the applied bias, am is the Information). Although the integration of the Al2O3 layer
mean hopping distance, ne is the density of space charge, vf is enhanced several parameters, including charge mobility and
the intrinsic vibration frequency, and k is Boltzmanns con- read Ion/Ioff by isolating the NPs from pentacene (Table S4,
stant. Thermally excited electrons in pentacene layer can hop Supporting Information), the memory window was reduced
from one trap state to another over barrier height between from 73.84 to 59.72 V. These results indicate that the addithe localized sites. In addition to hopping mechanism, carrier tional Al2O3 tunneling dielectric layer disrupts the transfer of
mobility may be increased as the interconnectivity between charge carriers into the CoFe2O4 NPs and the oleate layer is a
pentacene grains is improved as the substrate temperature sufficient tunneling layer in our NFGM devices.
increases, leading to the reduced number of traps at the grain
boundaries under a given channel length.[59] Furthermore,
hysteresis can be enhanced as the temperature increases due 2.3. Electrical Memory Characteristics of Flexible
to the fluctuation in the number of trapped charges resulting NFGM Devices
from the change in the values of qt and am, which are
affected by the gate voltage.[60]
The CoFe2O4 NP-embedded NFGM devices were prepared
on polyethylene terephthalate (PET) films to demonstrate
the low voltage operation and the feasibility of fabricating
2.2. Effects of an Additional Tunneling Dielectric Layer on
flexible organic memory devices since they are essential
Memory Characteristics
prerequisites for the practical application in flexible devices.
Most of the organic NFGM devices reported so far required
The outstanding electrical memory characteristics of gate voltages of at least 30 V for efficient field-effect modCoFe2O4 NP-based NFGM devices in the absence of a tun- ulation and maximization of the charge trap in NPs[12,53,64]
neling dielectric layer may be attributed to the exceptional and a small memory window less than 20 V was often
charge trapping and release capability of oleate-capped obtained at higher P/E operation voltage in flexible NFGM
(2 nm) CoFe2O4 NPs. A coating consisting of a SAM of devices.[6,22] Al2O3 dielectric layer (100 nm) was subsealkyl chains can act as an alternative tunneling dielectric layer quently deposited using radio-frequency (RF) sputtering.

a)

0.6

VGS (V)

b)

-ID (A)

read on

100

-ID (A)

-ID (A)

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program

VGS (V)

-ID (A)

-1

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The CoFe2O4 NPs and pentacene layer were deposited consecutively, followed by the formation of gold sourcedrain
electrodes. Figure 6 shows a schematic, photograph, and
electrical memory characteristics of the resulting flexible
NFGM devices. Despite the risks of current leakage and
performance degradation due to the high surface roughness and temperature susceptibility of the PET substrate,
the flexible NFGM devices exhibited excellent electrical
memory performance with a large memory window of over
32 V, even after 700 P/E cycles in low gatesource voltage
sweep between 20 and +20 V (Figure 6c,d, and Figure S9a,
Supporting Information). The mechanical stability of the
CoFe2O4 NP-based NFGM devices was tested by measuring
electrical memory performance after repeated bending
cycles. The tensile strain at the top surface (top) of the flexible memory devices can be calculated from the following
equation for a simple bending:[65]

thin-film (F) and substrate (S), respectively. top can be simply

calculated as DS/2R.
As shown in Figure 6e and Figure S9b (Supporting Information), the memory window was retained above 26 V over
500 bending cycles with minimal electrical degradation during
gatesource voltage sweeps between 20 V and +20 V against
a tensile strain of 0.54%. This strain was induced by a bending
radius of 7 mm, indicating that these devices have high potential for use in flexible or stretchable electronic devices. Conversely, a memory window smaller than 2 V was observed with
flexible devices prepared without CoFe2O4 NPs (Figure S9c,
Supporting Information). This confirmed that the CoFe2O4
NPs acted as charge trap sites for memory performance.

3. Conclusion

High-performance flexible organic NFGM devices were

(3) fabricated using pentacene and CoFe2O4 NPs as the semiconductor and charge trapping agent, respectively. Monodisperse CoFe2O4 NPs with three different diameters (5, 8, and
where = DF/DS and = YF/YS. R is the bending radius, D is 11 nm) were synthesized by a simple thermal decomposition
the thickness and YF and YS are the Youngs modulus of the method starting from a low-cost and non-toxic metaloleate
complex
precursor.
NFGM
devices based on 8 nm CoFe2O4
a)
b)
NPs exhibited the best electrical
memory performance due to
favorable energy levels and uniform dispersion on the substrate.
These factors resulted in a large
memory window of 73.84 V,
fast and reversible switching
behavior, a high read Ion/Ioff of
2.98 103, and outstanding
data retention, facilitated by an
d)
c) 10-7
oleate capping layer that acted
program
20
erase
as an alternative tunneling die-8
lectric layer. It is noteworthy
programmed state
10
10
that the electrical memory performance of the NFGM devices
0
-9
based on CoFe2O4 NPs was
10
-10
erased state
comparable to that of Au NPembedded ones. Furthermore,
-10
-20
10
the NFGM devices were electri0 200 400 600 800
-20 -10 0 10 20
cally and mechanically stable on
VGS (V)
P/E cycles
flexible PET substrates at low
operation voltage and retained
e)
a memory window over 32 and
20
26 V with little electrical degraprogrammed state
10
dation after 700 P/E cycles and
500 bending cycles, respectively.
0
Solution-processed,
monodiserased state
perse CoFe2O4 NPs allowed
-10
simple and cost-effective deposition of nano-floating gates
-20
0 100 200 300 400 500
with controllable size and denbending cycles
sity, which has been challenging
in the fabrication processes of
Figure 6. a) A schematic image, b) photograph, c) transfer curves (at VDS = 20 V), d) electrical, and
NFGM devices.
e) mechanical stability test of the flexible NFGM devices based on 8 nm CoFe O NPs on PET substrate.

Vt

Vt

-ID (A)

( DF + DS ) (1 + 2 + 2 ) Ds
top =

2R
2 R (1 + ) (1 + )

2 4

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DOI: 10.1002/smll.201501382

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full papers
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In addition, the oleate capping layer significantly simplified the fabrication process by eliminating the need for an
additional tunneling dielectric layer. Our findings demonstrate that sophisticated control of methodologies when synthesizing semiconducting or metal oxide NPs can yield novel
charge trapping agents for memory devices and open up new
possibilities for the simple and low-cost fabrication of highperformance data storage devices.

4. Experimental Section
Synthesis of (Co2+Fe23+)Oleate Precursor: FeCl36H2O
(8.64 g, 32 mmol), CoCl26H2O (3.808 g, 16 mmol), and sodium
oleate (38.96 g, 128 mmol) were dissolved in a mixture of 80 mL
of ethanol, 80 mL of D. I. water, and 160 mL of n-hexane. The
solution was stirred until all the reagents were dissolved completely. Then, the solution was refluxed at 60 C for 4 h. The
reacted (Co2+Fe23+)oleate was washed three times with 120 mL
of D. I. water and residual solvent was evaporated in the rotary
evaporator at 80 C.
Synthesis of 8 nm CoFe2O4 NPs: (Co2+Fe23+)oleate complex
(2.5 g), OLA (0.25 g), and octadecene (10 mL) were mixed and
evacuated at 80 C for 1 h. The mixture was stirred with Ar bubbling at rising temperature. After 30 min, the mixture was heated
to 310 C at a heating rate of 1 C min1 and maintained at this
temperature for 1 h. The reacted solution was cooled to room
temperature and washed three times with acetone/ethanol mixture. Finally, the purified CoFe2O4 NPs were dispersed in 10 mL of
n-hexane for long-term storage.
CoFe2O4 NPs in different sizes can be synthesized by the same
procedures, except for the Ar bubbling flow rate, which optimizes
the NP size. 5 nm CoFe2O4 NPs were synthesized under vigorous Ar
bubbling. Reversely, 11 nm ones were synthesized when Ar bubbling was stopped before the solution was heated.
NFGM Device Fabrication: CoFe2O4 NP solution (2 mg mL1) was
spin-coated at 1000 rpm for 60 s on the OTS-treated Si/SiO2 wafer
(D. I. water contact angle: 107 (Figure S10, Supporting Information))[66,67] and annealed at 60 C for 3 h in the vacuum oven to
evaporate the solvent thoroughly. 50 nm thick pentacene was thermally deposited on the surface of NPs at a rate of 0.010.03 nm s1
at 60 C (substrate temperature) under a pressure of 5.0 106 Torr.
Gold sourcedrain electrodes (40 nm) were also thermally deposited in the evaporation chamber at room temperature using shadow
masks with 50 m of channel length (L) and 1000 m of channel
width (W). For the flexible NFGM device fabrication, 100 nm thick
Al2O3 gate dielectric layer was deposited on the PET substrate by
RF sputtering technique after the gate electrode (Cr (5 nm)/Au (100
nm)) was formed by thermal evaporation. The other processes are
the same as those in the fabrication on the Si wafer as described
above. Additional tunneling dielectric layer, 10 nm Al2O3 thin film
was deposited by ALD at a substrate temperature of 150 C.
Energy Level Measurement: All the cyclic voltammetry (CV)
measurements were performed in 0.1 m of tetabutylammonium
hexafluorophosphate (Bu4NPF6) in anhydrous acetonitrile electrolyte at room temperature at a scan rate of 100 mV s1 under
N2 gas blowing for the estimation of the valence band energy
level of the CoFe2O4 NPs. CoFe2O4 NP solution was deposited on
indium tin oxide (ITO) glass and used as a working electrode.

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The counter electrode and the reference electrode were platinum

(Pt) wire and Ag/Ag+ electrode containing 0.01 m of AgNO3 with
0.1 m of tetrabutyl ammonium perchlorate (TBAP) in acetonitrile,
respectively. The Ag/Ag+ reference electrode was internally calibrated by ferrocene/ferrocenium couple (Fc/Fc+) and the valence
band energy level of NPs can be estimated using:
E valenceband (eV ) = E (onset
E (onset
+ 4.8
ferrocene )
ox )

(4)

For the estimation of the energy bandgap of CoFe2O4 NPs,

both NP solution and spin- coated samples were measured using
double-beam mode. The sample for the solution-based UVvis
absorption spectrum was prepared by diluting 100 L of extracted
5, 8, and 11 nm CoFe2O4 NP solution in 3 mL of n-hexane. For the
spin-coated samples, UVvis absorption spectra can be obtained
by similar procedures except the quartz cuvette was replaced with
quartz plate which was spin-coated at 1000 rpm using of CoFe2O4
NP solution (10 mg mL1) before loaded on the sample holder.
Instruments for Characterization: All the electrical performances of the NFGM devices were measured in an N2-filled glove
box using a Keithley 4200 semiconductor parametric analyzer.
The size and shape of NPs were characterized using transmission electron microscopy (TEM; JEM-2100, JEOL) operated at 200 kV.
Specimens for TEM were prepared by conventional methods, dropping the diluted CoFe2O4 NP solution onto the copper grid. Inverse
spinel structure of NPs was characterized using X-ray diffraction
(Figure S6, Supporting Information, XRD; Bruker, Germany). Rotating
anode was used as X-ray source, and the measurement was operated at 220 V. The sample was prepared in the form of solid powder.
For the surface analysis of the NFGM devices, tapping-mode
atomic force microscope (AFM; Veeco (USA)) was used and the
sample for cross-sectional STEM analysis was prepared using
dual-beam focused ion beam (FIB, Helios 450 HP, FEI, USA) on the
copper grid and analyzed with high-resolution transmission electron microscope (HR-TEM, Cs-corrected JEM-2100F, JEOL, Japan).
The bandgaps of CoFe2O4 NPs were measured using UV-1800 (Shimadzu Corp.) and VARIAN CARY 100 (Agilent Tech).

Supporting Information
Supporting Information is available from the Wiley Online Library
or from the author.

Acknowledgements
This work was supported by the Center for Advanced Soft
Electronics under the Global Frontier Research Program
(2013M3A6A5073175), the National Research Foundation of Korea
(2014R1A2A2A01007467) of the Ministry of Science, ICT & Future
Planning, Korea, and the New & Renewable Energy Core Technology
Program (20133030000180) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted nancial resource
from the Ministry of Trade, Industry & Energy, Korea. J.H.J. acknowledges Moo Yeol Lee for his help in drawing 3D illustrations.

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