nanomaterials

Article
Memristic Characteristics from Bistable to
Tristable Memory with Controllable Charge
Trap Carbon Nanotubes
Lei Li * ID
and Dianzhong Wen *
Key Laboratories of Senior-Education for Electronic Engineering, Heilongjiang University, Harbin 150080, China
* Correspondence: lileidtk@hlju.edu.cn (L.L.); wendianzhong@hlju.edu.cn (D.W.);
Tel.: +86-451-8660-4985 (L.L. & D.W.)

Received: 12 January 2018; Accepted: 13 February 2018; Published: 17 February 2018

Abstract: The incorporation of the one-dimensional carbon nanomaterial carbon nanotubes (CNTs)
in poly(methyl methacrylate) (PMMA) was found to successfully develop a resistive switching.
It implements memristic characteristics which shift from bistable to tristable memory. The localized
current pathways in the organic nanocomposite layers for each intermediate resistive state (IRS)
are attributed to the trapping mechanism consistent with the fluorescent measurements. Multi-bit
organic memories have attracted considerable interest, which provide an effective way to increase
the memory density per unit cell area. This study will be useful for the development and tuning of
multi-bit storable organic nanocomposite memory device systems.

Keywords: tristable memory; memristic characteristics; multi-bit; fluorescence spectrum

1. Introduction
Intelligent functional materials designed for organic memory devices, fueled by information
explosion, must cater to ultra-high-density data storage [1,2]. In fact, optical and magnetic storage
technologies based on inorganic semiconductors traditionally suffer from a variety of restrictions,
including an incremental demand for memory materials together with downscaling of the cell
size. The advent of resistive random-access memories (RRAMs), as one of the most prominent
transformations, has played a critical role in favor of structure simplicity, layer-by-layer stacking,
low power consumption, and capability for the storage of multi-conductive states [3,4]. Multi-bit
organic memories have attracted considerable interest for their high data storage capacity. In spite of
advances, the search for multi-bit memory materials still remains a formidable challenge. The majority
of research on organic memory devices has been concentrated on binary memory with bistably
electronic organic materials. Tremendous efforts have been made to develop a variety of memory
materials and boost the memory performance of devices such as a high OFF/ON ratio, long-term
retention, and switching speed. The capability for multi-bit information storage provides an effective
way to increase the memory density per unit cell area.
In light of electrical bistability, existing organic memory devices primarily accommodate in
a binary system with the data storage capacity limited to 2n . Exceeding two conductive states in
memory devices can be considered as one of the most effective methods to boost the data storage [5–14].
Several organic memory devices have recently been reported to fulfill ternary memory behavior under
an external electric field, which facilitates a powerful increase in data-storage density. Multi-bit
memories dependent on small molecules with a D-A structure are found in organometallics with two
or more reversible oxidation states. Nevertheless, memories based on polymer offer several benefits,
including solution processing and higher structural diversity. In contrast with binary memories,
multi-bit memories are much more challenging, as suitable materials are not accessible and the

Nanomaterials 2018, 8, 114; doi:10.3390/nano8020114 www.mdpi.com/journal/nanomaterials

Nanomaterials 2018, 8, 114 2 of 11

underlying mechanisms are controversial. Many mechanisms have been applied to explain the
performance of organic storage behaviors, including metal-filament formation, field-induced charge
transfer, molecular redox, conformational change, and charge trapping. It has been theorized that
ternary storage materials containing different trap depths may be a precondition for storage [15–20].
Various traps have a critical role in the formation of conducting paths in the organic active layers by
comparing current–voltage characteristics with well-established charge transport mechanisms, such as
Poole–Frenkel conduction, space charge limited current, and Fowler–Nordheim tunneling.
In this study, for further investigation, the changes of the memristic characteristics with different
contents of carbon nanotubes (CNTs) were observed in the composite of PMMA and CNTs. For resistive
memory systems established by nanocomposite materials, organic/inorganic nanoclusters embedded
in organic matrices can be perceived as the charge trapping elements. More specifically, this paper aims
to observe the electronic dynamics, thereby enabling a better understanding of memristic characteristics
from bistable to tristable memory in organic nanocomposite memory systems.

2. Materials and Methods

The COOH-functionalized multiwalled carbon nanotubes (MWCNT-COOH) were purchased
from Hengqiu Tech. Inc., Suzhou, China, the carboxylic content of which reached 2 wt %.
The nanocomposites of PMMA (purchased from ARKEMA, Colombes, France) and MWCNT-COOH
were spin-coated on indium tin oxide (ITO)-coated glass substrates to manufacture resistive switching
memory devices. Firstly, the ITO-coated glass substrates whose conductivity ranged from 6 Ω/sq to
9 Ω/sq were ultrasonicated for 1 h, and were successively cleaned in acetone, methanol, and ethanol
solvents. The insulating polymer, PMMA, was dissolved in a chloroform (10 mg/mL) solution.
Different weight % of MWCNT-COOH were added to the PMMA solution. After that, the mixed
solution of PMMA and MWCNT-COOH was ultrasonicated for 2 h, then spun on ITO substrates at
a speed of 3000 rpm for 60 s. Next, the hybrid films consisting of PMMA and MWCNT-COOH were
prepared on ITO-coated glass substrates in ambient air. To evaporate solvents, the films were kept at
60 ◦ C for 24 h in vacuum. Subsequently, a 300-nm-thick Ni layer was deposited on top of the thin film
at room temperature (300 K) by thermal evaporation technique with a shadow mask. The evaporation
was performed at 1 × 10−5 Torr of pressure.
An FEI Sirion (Philips, Holland, The Netherlands) field emission scanning electron microscope
(FESEM) was used to characterize the cross-section of the hybrid films with MWCNT-COOH dispersed
in polymer matrix. A NanoMap 500LS 3D Profilometer (aep Technology, Santa Clara, CA, USA) was
adopted to measure the thickness of the hybrid films. Micrographs of MWCNT-COOH embedded in
polymer were acquired using a JEM-2100 (JOEL, Tokyo, Japan) transmission electron microscopy (TEM).
Raman spectroscopy (LabRam HR800 Raman Spectrometer; Horiba Jobin Yvon, Villeneuve-d’Ascq,
France) was coupled with an Olympus BX41 microscope fitted with 50× objective, employing
a 514.5 nm laser source. The spectral resolution was 0.35 cm−1 , while the spatial resolution was 1 µm
and 2 µm, respectively, from horizontal and vertical angles. The spectral peaks were fitted by Gaussian
model with the program Origin 8.0. Thermogravimetric analysis (TGA; TA Instruments, New Castle,
DE, USA) and differential scanning calorimetry (DSC; TA Instruments, USA) were used to analyze
the thermal properties of MWCNT-COOH. TGA was implemented under a nitrogen atmosphere
at heating rates of 10 ◦ C/min, 15 ◦ C/min, and 20 ◦ C/min. An AVENTES fiber optic spectrometer
(AvaSpec-HS1024×58TEC-USB2 and AvaSpec-NIR256-1.7TEC; Avantes, Holland, The Netherlands)
was used to record. The electrical characteristics of the MWCNT-COOH-based resistive switching
were measured by a semiconductor parameter analyzer (Keithley 4200SCS; Keithley, Solon, OH, USA)
at ambient temperature. During electrical measurements of the memory devices, the Ni top layer was
grounded, while an electrical bias was applied to the ITO bottom electrodes. All measurements of the
devices were conducted under ambient conditions, without any encapsulation.
Nanomaterials 2018, 8, 114 3 of 11
Nanomaterials 2018, 8, 114 3 of 11

3. Results and Discussion

3. Results and Discussion
3.1. TGA, DSC, and Raman Measurement
3.1. TGA, DSC, and Raman Measurement
The structure of PMMA and a schematic representation of MWCNT-COOH are indicated
in Figure 1a. Theofmolecular
The structure PMMA andstructure a schematic of PMMA is a linear
representation polymeric chain
of MWCNT-COOH of methyl
are indicated in
methacrylate
Figure 1a. Themonomers, which act
molecular structure ofas the constitutional
PMMA unit. Forchain
is a linear polymeric MWCNTs,of methylthe combination
methacrylate
between adjacent
monomers, which actcarbon
as theatoms is in the unit.
constitutional formFor of the C-C covalent
MWCNTs, bond, which
the combination is one
between of the
adjacent
strongest
carbon atoms chemical
is in thebonds.
form of The the C-CITO/PMMA:MWCNT-COOH/Ni
covalent bond, which is one of thesandwiched structure
strongest chemical bonds. is
shown
The in FigureMWCNT-COOH/Ni
ITO/PMMA: 1b. The cross-section of the structure
sandwiched nanocomposite
is shown film with1b.1%,
in Figure The2%, and 3%
cross-section
MWCNT-COOH
of the nanocomposite contentfilm was
withcharacterized
1%, 2%, and 3% by FESEM,
MWCNT-COOH and the content
corresponding micrographs
was characterized by
are shown
FESEM, and inthe
Figure 2. A profilometer
corresponding was used
micrographs are to measure
shown the thickness
in Figure of all the films,
2. A profilometer was usedwhich to
was estimated
measure the thickness to of beall30 the nm.
films, Figure
which was 3a estimated
shows to TGAbe 30curves
nm. Figureof 3atheshows
corresponding
TGA curves
PMMA:MWCNT-COOH
of the corresponding PMMA: nanocomposites.
MWCNT-COOH Based on this figure,
nanocomposites. all on
Based of them exhibited
this figure, a them
all of good
thermal stability
exhibited with a stability
a good thermal weight losswithof about 5%
a weight loss at
of the
about decomposition temperatures
5% at the decomposition of 145 °C
temperatures
of 145 ◦ C (PMMA: 1%MWCNT-COOH),
(PMMA:1%MWCNT-COOH), 140 140 °C ◦ C(PMMA:2%MWCNT-COOH),
(PMMA: 2%MWCNT-COOH), andand 132 ◦ C132(PMMA: °C
(PMMA:3%MWCNT-COOH).
3%MWCNT-COOH). It exhibited aIttwo-step
exhibited a two-step
degradation: thedegradation:
first step was duethe to
first
thestep was
loss of due to
remaining
the loss
water of remaining
molecules water molecules
and oxygenating functionaland oxygenating
groups. The second functional
degradationgroups. The second
step (370–450 ◦ C)

degradation
involved the step (370–450
pyrolysis of the °C)remaining
involved oxygen-containing
the pyrolysis of the remaining
groups as welloxygen-containing
as the burning of
groups
the ringas well as
carbon theItburning
[21]. can be of seenthethat
ringthecarbon [21]. It can be
nanocomposites seen thatdegraded
completely at ~400 ◦ C.
the nanocomposites
completely
DSC degraded
measurements of at the~400 °C. DSC measurements
nanocomposites were performed, of theand nanocomposites were performed,
the results obtained are shown
and the results obtained are shown in Figure 3b. The figure illustrates
in Figure 3b. The figure illustrates the corresponding glass-transition process at Tg = 121.0 C, 130.1 the ◦
corresponding ◦ C,
glass-
transition ◦
122.7 process
C, the at Tg = 121.0 °C, 130.1 °C, temperatures
and 122.7 °C, the of Tcorresponding ◦ ◦ ◦
and corresponding melting m = 143.6 C, melting
151.3 C, temperatures
and 145.4 of C,
Tm = the
and 143.6 °C, 151.3 °C,melting
corresponding and 145.4 °C, and∆H
enthalpies themcorresponding
= 143.8 J/g, 105.6 melting
J/g, enthalpies
and 106.9 J/g, ΔHmrespectively.
= 143.8 J/g,
105.6 J/g,spectrum
Raman and 106.9measurements
J/g, respectively. of Raman spectrum measurements
the as-prepared hybrid films with of the as-prepared
different masshybrid
weights filmsof
with different mass
MWCNT-COOH wereweights
performed,of MWCNT-COOH
as shown in Figure were3c.performed,
The Raman as shown
spectra withinspecific
Figurepeaks3c. Thefor
Raman spectra
MWCNTs include with specific
a D-band andpeaks for MWCNTs
a G-band. A shift ofinclude
the D peak a D-band and a G-band.
of MWCNTs A shift of
arose separately at
the D
1364 −
cmpeak1 of cm
, 1366 −
MWCNTs1 , and 1370arose − 1
cmseparately at 1364 cm
as the incremental −1
content, 1366 cm , and 1370 while
−1
of MWCNT-COOH, cm−1 as thatthe of
incremental
the content of
G peak happened MWCNT-COOH,
separately at 1578 cm − 1 , 1582
while that cm −1,G
of the andpeak1586 cm− 1 . The
happened separately
shift may at 1578 cm−1,
be related
1582
to thecm −1, and 1586 cm−1. The shift may be related to the increased concentration of CNTs. For
increased concentration of CNTs. For all of the nanocomposite films with 1%, 2%, and 3%
all of the nanocomposite
MWCNT-COOH, films with
the corresponding 1%, 2%,
intensity and
ratio 3% D
of the MWCNT-COOH,
and G bands ID /Ithe G was corresponding
calculated to
intensity
be 0.86. ratio of the D and G bands ID/IG was calculated to be 0.86.

Figure 1.
Figure 1. Resistive
Resistive switching of indium
switching of indium tin
tin oxide
oxide (ITO)/PMMA:MWCNT-COOH/Ni.
(ITO)/PMMA:MWCNT-COOH/Ni. (a) (a) The
The structure
structure
of PMMA and a schematic representation of MWCNT-COOH; (b) Configuration of the
of PMMA and a schematic representation of MWCNT-COOH; (b) Configuration of the sandwiched sandwiched
resistiveswitching
resistive switching ITO/PMMA:MWCNT-COOH/Ni.
ITO/PMMA:MWCNT-COOH/Ni. MWCNT-COOH:
MWCNT-COOH: COOH-functionalised
COOH-functionalised multiwalled
multiwalled
carbon carbon
nanotube; nanotube;
PMMA: PMMA: methacrylate).
poly(methyl poly(methyl methacrylate).
Nanomaterials 2018, 8, 114 4 of 11
Nanomaterials 2018, 8, 114 4 of 11
Nanomaterials 2018, 8, 114 4 of 11

Figure 2. Cross-sectional field emission scanning electron microscope (FESEM) images of

Figure 2. Cross-sectional field emission scanning electron microscope (FESEM) images of
Figure 2. Cross-sectionalnanocomposite
PMMA:MWCNT-COOH field emission
filmsscanning electroncontents
with the distinct microscope (FESEM) images
of MWCNT-COOH (a) 1%, of
PMMA:MWCNT-COOH
PMMA:MWCNT-COOH nanocompositefilms
nanocomposite filmswith
withthe
thedistinct
distinct contents
contents of MWCNT-COOH
of MWCNT-COOH (a) 1%;
(a) 1%,
(b) 2%, and (c) 3%, respectively.
(b) 2%; and (c) 3%, respectively.
(b) 2%, and (c) 3%, respectively.

Figure 3. (a) Thermogravimetric analysis (TGA) curves and (b) Differential scanning calorimetry
(DSC) curves at a heating rate of 10 ℃ min−1, measured in a nitrogen atmosphere, for the
nanocomposites with the mass weight 1%, 2%, and 3% of MWCNT-COOH; (c) Raman spectra of the
Figure
Figure 3.3.(a)
hybrid
(a) Thermogravimetric analysis (TGA) curves and (b) Differential scanning calorimetry
Thermogravimetric
films analysis
with the different mass (TGA)
weight curves and (b) Differential scanning calorimetry (DSC)
of MWCNT-COOH.
(DSC) curves at a heating rate of 10 ℃ min , measured in a nitrogen atmosphere, for the
−1
curves at a heating rate of 10 °C·min−1 , measured in a nitrogen atmosphere, for the nanocomposites
nanocomposites with the mass weight 1%, 2%, and 3% of MWCNT-COOH; (c) Raman spectra of the
with the mass weight 1%, 2%, and 3% of MWCNT-COOH; (c) Raman spectra of the hybrid films with
hybrid films with the different mass weight of MWCNT-COOH.
the different mass weight of MWCNT-COOH.
Nanomaterials 2018, 8, 114 5 of 11
Nanomaterials 2018, 8, 114 5 of 11
3.2. Current–Voltage (I–V) Characteristics of the Memory Devices
In this work, we have also investigated how MWCNT-COOH content would impact on
3.2. Current–Voltage (I–V) Characteristics of the Memory Devices
the memory performance of ITO/PMMA:MWCNT-COOH/Ni. The memristic characteristics
In this work,
are illustrated we have
in Figure 4. also investigated how MWCNT-COOH content would impact on
the memory
A typical I–V curve ofofthe
performance ITO/PMMA:MWCNT-COOH/Ni.
resistive switching with 1% MWCNT-COOH The memristic characteristics
is demonstrated are
illustrated
in Figure 4a. in Figure
During 4. the applied voltage sweep, the measured current values were plotted in
A typicalscale,
a logarithmic I–V curve of the
with the resistive switching
compliance current kept with in1% MWCNT-COOH
check is demonstrated
at 10−1 A. It implements a binary in
Figure 4a. During the applied voltage sweep, the measured
write-once read-many-times (WORM) memory behavior with an ON/OFF current ratio current values were plotted in a logarithmic
scale, with
greater thanthe 10compliance
7. At first, thecurrent kept switching
resistive in check atwas 10−in1 A. It implements a binary write-once
a high resistance state (HRS or “0”
read-many-times (WORM) memory behavior with an ON/OFF current ratio greater thanV10 7 At first,
state) with current levels of 10 –10 A. The current surged at
−10 −9 the threshold voltage th =. −3.9 V,
the resistive
switching fromswitching
OFF-state wastoinON-state.
a high resistance
Then, the state (HRS
device or “0” astate)
retained low with current
resistance levels
state (LRS of
− 10
10 “1” − 9
–10state),A. The currentapplying
surged atathe threshold voltage −3.9
V th = or V, switching from
or whether reverse voltage sweep even removing theOFF-state
applied
to ON-state. Then, the device retained a low resistance state (LRS
electrical field. The transition between HRS (OFF-state or “0” state) and LRS (ON-state or “1”or “1” state), whether applying
a reverse
state) wasvoltage
switchable sweepand or even removing
bistable. Then,the theapplied
sample electrical
was kept field. The lab
in the transition
atmospherebetween HRS
where
(OFF-state
the humidity or “0” andstate) and LRS (ON-state
temperature of the test or “1” state)
could bewas switchableinand
maintained thebistable. Then, the sample
same condition. After
was kept
two months in the lab atmosphere
(sweep 5), the same wherecellthe
was humidity
measuredandagain,
temperature
sweeping of thefrom
test could
−6 V to be 6maintained
V, which
in the same
remained incondition.
the ON-state. AfterThe
tworetention
months (sweep 5), the same
characteristics of thecell
ON was andmeasured
OFF states again,
showedsweepingthat
from − 6 V to 6 V, which remained in the ON-state. The retention characteristics
the ON state was stable beyond 10 s under a constant stress of −1 V (Figure 4b). We measured
5 of the ON and OFF
states showed that the ON state was stable beyond 10 5 s under a constant stress of −1 V (Figure 4b).
twenty cells of ITO/PMMA:MWCNT-COOH/Ni to evaluate the repeatability of I–V
We measured twenty
characteristics. cells of ITO/PMMA:MWCNT-COOH/Ni
At a voltage of −1 V, Figure 4c shows the device-to-deviceto evaluate the repeatability
profile of IONofand I–V
characteristics. At a voltage of − 1 V, Figure 4c shows the device-to-device
IOFF without considerable deviations. The primary devices exhibited binaryONelectrical profile of I and I OFF
without considerable
transition signals with deviations.
no ternary Theperformance
primary devices exhibited
observed. binary
In the electrical
inset, Vth of transition
the devices signals
was
with nolocated
mostly ternary from performance
−2.9 V to observed.
−5.7 V. The In the inset, V th of the
reproducibility of devices was mostly located
MWCNT-COOH-based from
cells is
− 2.9 V to − 5.7 V. The reproducibility of MWCNT-COOH-based cells
feasible for the reliable resistive switching with high ON/OFF ratio. Owing to the insulatingis feasible for the reliable resistive
switching
nature of with
purehigh PMMA,ON/OFF ratio. Owing
the hybrid to theainsulating
film with doping level nature ofofMWCNT-COOH
pure PMMA, the hybrid below film 1%
with a doping level
performed as an insulator. of MWCNT-COOH below 1% performed as an insulator.

Figure
Figure 4.4.Memristic
Memristiccharacteristics of ITO/PMMA:MWCNT-COOH/Ni
characteristics of ITO/PMMA:MWCNT-COOH/Ni with thewith
content
theofcontent
MWCNT- of
COOH 1%. (a) I–V characteristics; (b) Retention characteristics for ON and OFF
MWCNT-COOH 1%. (a) I–V characteristics; (b) Retention characteristics for ON and OFF states under a constant
states
stress
underof -1 V; (c) Device-to-Device
a constant stress of −1 V; (c)distribution of ION distribution
Device-to-Device and IOFF, andofVIth in and
Inset.
I , and V in Inset.
ON OFF th
Nanomaterials 2018, 8, 114 6 of 11
Nanomaterials 2018, 8, 114 6 of 11
Compared with the 1% MWCNT-COOH film, the memristic characteristics of the hybrid
film with 2% of MWCNT-COOH presented tristable memory behavior, shown in Figure 5. As
for itsCompared with the 1%the
I–V characteristics, MWCNT-COOH
device initiallyfilm, the memristic
exhibited characteristics
HRS (OFF-state or “0” of state).
the hybrid
When filma
with 2% of MWCNT-COOH presented tristable memory behavior,
negative voltage (0 to −6 V, sweep 1) was applied to the ITO electrode, two abrupt current shown in Figure 5. As for its I–V
characteristics,
increases werethe device initially
observed exhibited
at switching HRS (OFF-state
threshold voltagesorof“0” state).
Vth1 = −2.6When V anda negative voltage
Vth2 = −4.2 V,
(0 to −6 V, sweep
indicating that the 1) was
deviceapplied
wenttothrough
the ITO electrode, two abrupt
disrupt electrical current increases
transitions were observed
from OFF-state to an
at switching threshold voltages
intermediate-conductive stateof V th1 = −2.6orV “1”
(ON1-state V th2 = −
and state), 4.2 V,
and indicating
then to LRSthat the device
(ON2-state orwent
“2”
throughThe
state). disrupt
cell electrical
remainedtransitions
LRS during fromaOFF-state
subsequent to anscan
intermediate-conductive
from 0 to −6 V (sweep state2),
(ON1-state
even after or
“1” state), and then to LRS (ON2-state or “2” state). The cell remained
the power was turned off or by applying a reverse bias (sweep 3 and sweep 4). The result LRS during a subsequent scan
suggests −6 Vthe
from 0 to that (sweep 2), even
resistive after thewith
switching power was turned
content off or by applying
of MWCNT-COOH 2% acanreverse bias (sweep
be employed as
3 and sweep
ternary WORM 4). The resultThe
device. suggests thatratios
current the resistive
of threeswitching
distinctwith content ofstates
conductive MWCNT-COOH
were roughly 2%
can be
1:10 3:10employed
7, identical as with
ternary“0”,WORM device.
“1”, and The current
“2” states. ratiosstates
All three of three distinct conductive
presented good stability states were
under
3 7
aroughly 1:10of
stress test :10−1, Videntical
for the with “0”, “1”,
retention timeand “2” states.
beyond 10 s, All
5 three states
exhibited presented
in Figure 5b. No good stability
significant
under a stress in of −1 Vfor
testcurrent for “0”,
the retention time 5 s, exhibited in Figure 5b. No significant
degradation “1”, and “2”beyond
states10 was seen during the test. Besides the
degradationcell
individual in current for “0”, “1”,
performance, and “2” states was
the reproductivity of seen during the has
I–V behaviors test.been
Besides the individual
considered cell
as well.
Iperformance,
ON2, ION1, and OFF at V = −1ofVI–V
theIreproductivity behaviors
(for has beenare
each device) considered
depictedasin well. ION2 , 5c.
Figure ION1For IOFF at
, andtwenty
V = − 1 V (for each device) are depicted in Figure 5c. For twenty
independent cells, Vth1 was found to be in the range from −1.9 V to −3.1 V, and Vth2 independent cells, V was found
th1was between to
be in V
−3.8 theand
range−5.1fromV,−showing
1.9 V to −reasonable
3.1 V, and V th2 was between
separations −3.8 V and
between the − two5.1 V, showing reasonable
switching threshold
separations
voltages, asbetween
plotted in theInset.
two switching threshold voltages,
The distinguishable as plotted
two threshold in Inset.long
voltages, The retention
distinguishable
time,
two threshold voltages, long retention time, and good reproducibility
and good reproducibility of three conductivity states demonstrate that it is a promising of three conductivity states
demonstrate
candidate that itmaterial
active is a promising candidate
for ternary active
resistive material
memory for ternary
devices. resistivetemperature,
At ambient memory devices. the
At ambient
electrical temperature,of
measurement the electrical
the multi-bit measurement of the multi-bit
resistive switching was carriedresistive
out switching
in air. With was carried
a further
out in air.inWith
increase a further
the content of increase
MWCNT-COOH in the content(3%),ofitMWCNT-COOH
showed only a single (3%), high-conductivity
it showed only a single state
high-conductivity
without switchingstate without switching
phenomenon (Figurephenomenon (Figure
6). This indicates 6). This
that indicates
the device hadthat
nothe device
data had
storage
no data storage ability. In summary, the electrical properties
ability. In summary, the electrical properties of PMMA:MWCNT-COOH devices varied from of PMMA:MWCNT-COOH devices
varied from
bistable bistablememory
to tristable to tristable memory
behavior and behavior
furtherand further to behavior
to conductor conductorwith behavior with increasing
increasing MWCNT
MWCNT content.
content.

Figure
Figure 5.5.Memristic
Memristic characteristics of ITO/PMMA:MWCNT-COOH/Ni
characteristics of ITO/PMMA:MWCNT-COOH/Ni with thewith
content
theofcontent
MWCNT- of
COOH 2%. (a) I–V 2%.
MWCNT-COOH characteristics; (b) Retention (b)
(a) I–V characteristics; characteristics for ON and OFFfor
Retention characteristics states
ONunder
and OFFa constant
states
stress
under of −1 V; (c) stress
a constant Device-to-Device distribution of ION
of −1 V; (c) Device-to-Device and IOFF, and
distribution of IVth1 and
and IVth2 in theVinset.
, and and V in
ON OFF th1 th2
the inset.
Nanomaterials 2018, 8, 114 7 of 11
Nanomaterials 2018, 8, 114 7 of 11

6. I–V
Figure 6. I–Vcharacteristics
characteristics of ITO/PMMA:3%MWCNT-COOH/Ni
of ITO/PMMA:3%MWCNT-COOH/Ni withwith the content
the content of MWCNT-
of MWCNT-COOH.
COOH.
3.3. Proposed Memory Mechanisms
3.3. Proposed Memory Mechanisms
The one-dimensional carbon nanomaterial along its axis, CNTs, mostly affect the electrical
The one-dimensional
behavior of the hybrid films carbon
becausenanomaterial along its axis,
of the insulator-like PMMA. CNTs, To mostly affect into
gain insight the electrical
memory
behavior of the hybrid films because of the insulator-like PMMA.
behaviors from bistable to tristable states, TEM micrographs of pristine MWCNT-COOH are To gain insight into memory
behaviors
shown from bistable
in Figure 7a–c, in to tristable
which states, TEM
the samples micrographs ofwere
of MWCNT-COOH pristine MWCNT-COOH
ultrasonicated are
in ethanol.
shownfigures
These in Figure 7a–c, inthat
demonstrate which the MWCNT-COOH
pristine samples of MWCNT-COOH possesses several were ultrasonicated
micrometers of lengthin
ethanol. These figures demonstrate that pristine MWCNT-COOH
and several nanometers of diameter. It is comprised of multilayers of single-walled CNTs in the possesses several
micrometers
coaxial shell. Theof length
hybrid andfilmsseveral nanometers by
were manufactured of spin-coating
diameter. It theis comprised
nanocomposite of multilayers
solution with of
single-walled
2% MWCNT-COOH CNTsoninTEM the coaxial shell.7d,e
grids. Figure Theare hybrid films were
TEM images manufactured
of PMMA by spin-coating
and MWCNT-COOH blend
at different positions of the same TEM grid. The layer-to-layer distance approached7d,e
the nanocomposite solution with 2% MWCNT-COOH on TEM grids. Figure are TEM
the interlayer
images of
spacing of graphene
PMMA and 0.34 MWCNT-COOH
nm. It was observed blend
that at thedifferent
number of positions
multilayersof the same
ranged fromTEM 10 grid.
to 20.
Spin-casting of the nanocomposites on ITO substrates resulted in a thin hybrid film with planar was
The layer-to-layer distance approached the interlayer spacing of graphene 0.34 nm. It and
observed
random that theofnumber
orientation CNTs. The ofRaman
multilayers
spectrum ranged from 10 to possesses
of MWCNT-COOH 20. Spin-casting of the
two characteristic
nanocomposites
bands in Figure 8a.onThe ITO substrates
G peak at 1598.4resulted
cm−1 isinascribed
a thin hybrid film of
to E2g mode with planarinand
vibration random
the graphite
orientation of CNTs. The Raman spectrum of MWCNT-COOH possesses
planar, whose strength reflects the degree of graphitization. In addition, the D peak at 1380.3 cm−1 two characteristic
bands
is in Figure
associated with 8a. The G and
the defects peakthe atdisorder
1598.4 cm planeisofascribed
−1
MWCNT-COOH. to E2g mode of vibration
The intensity ratioinof the
the
graphite planar, whose strength reflects the degree of graphitization.
D and G bands ID /IG is an essential factor to evaluate the quality of CNTs. The ID /IG ratio was In addition, the D peak
at 1380.3 cm
estimated to beis0.78,
−1 associated with thethat
which indicates defects and the
the tubes were disorder plane
crystalline of MWCNT-COOH.
in nature [22]. Different from The
intensity ratio of the D and G bands I D/IG is an essential factor to evaluate the quality of CNTs.
CNTs, the ratio ID /IG for the hybrid films in Figure 3c may be influenced by the PMMA component.
The Ithe
With D/IG ratio was estimated to be 0.78,◦ which indicates
range of rising temperature from 40 C to 800 ◦ C, TGA curves that the tubes were crystalline
of MWCNT-COOH in Figure 8b in
nature [22]. Different from CNTs, the ratio I D/IG for the hybrid films in◦ Figure 3c may
illustrate that MWCNT-COOH were relatively active at heating rates of 10 C/min, 15 C/min ◦ be
influenced
and 20 ◦ C/min.by the PMMA
It was foundcomponent.
that the samples With of the range of rising
MWCNT-COOH temperature
exhibited from 40
good thermal °C to
stability,
800 °C, TGA curves of MWCNT-COOH ◦ in Figure
◦ 8b illustrate
◦
with the 5%-mass-loss temperature at 338 C, 348 C, and 362 C, respectively. The carboxylic group that MWCNT-COOH were
relatively active at heating rates of 10
successively decomposed when the weight loss continued until 800 C. This process stems from the
°C/min, 15 °C/min and 20 ◦°C/min. It was found that the
samples of MWCNT-COOH exhibited good thermal stability,
oxidation reaction of MWCNT-COOH, which was not completely oxidized, since the weight loss of with the 5%-mass-loss
temperature at 338
MWCNT-COOH was °C,
in the348 °C, and
range 362 °C,
of 18–21% respectively.
at 800 ◦ C. The carboxylic group successively
decomposed when the weight loss continued
In order to investigate the interaction between PMMA °C. until 800 and This process stems
MWCNT-COOH, fromfiber
optical the
oxidation reaction
spectroscopic of MWCNT-COOH,
experiments were conducted, which was not
scanning from completely
300–550 nm, oxidized,
and thesince
results theobtained
weight
loss of MWCNT-COOH was in the range of 18–21% at 800 °C.
are shown in Figure 9. In these experiments, the optical fiber of the spectroscope was placed
In order to
perpendicular toinvestigate the interaction
that of the light source. For between
the homogeneousPMMA and MWCNT-COOH,
solution of PMMA:MWCNT-COOHoptical fiber
spectroscopic experiments were conducted, scanning
blends (10 mg/mL), Figure 9 demonstrates the fluorescence spectra associated with from 300–550nm, and thetheresults
mass
obtained are shown in Figure 9. In these experiments, the optical
fraction of MWCNT-COOH 1%, 2%, and 3%. After varying the content of MWCNTs, the quenching fiber of the spectroscope was
placed perpendicular
phenomena were observed to from
that theof fluorescence
the light source. For the
spectra with homogeneous
the optical excitation solution
wavelength of
PMMA:MWCNT-COOH blends (10 mg/mL), Figure 9 demonstrates
390 nm. MWCNT-COOH hardly leads to the conformation change of PMMA, with the fact that the fluorescence spectra
associated
neither with nor
red shift thebluemass fraction
shift of the of MWCNT-COOH
maximal excited wavelength1%, 2%,was andobserved
3%. After varyingmass
in various the
content of MWCNTs, the quenching phenomena were observed from the fluorescence spectra
with the optical excitation wavelength 390 nm. MWCNT-COOH hardly leads to the
conformation change of PMMA, with the fact that neither red shift nor blue shift of the
Nanomaterials 2018, 8, 114 8 of 11
Nanomaterials 2018,8,8,114
Nanomaterials2018, 114 88of
of11
11

maximal excited wavelength was observed in various mass fractions of MWCNT-COOH. A

maximal excited wavelength was observed in various mass fractions of MWCNT-COOH. A
number of MWCNT-COOH.
fractions fluorescent polymers exhibit
A number of high sensitivity
fluorescent to CNTs
polymers quenchers,
exhibit anticipated
high sensitivity to
to CNTs
number of fluorescent polymers exhibit high sensitivity to CNTs quenchers, anticipated to
quench fluorescence
quenchers, anticipated bytoelectron
quench or energy transfer
fluorescence by [23–28].
electron or When
energythe quenching
transfer effect
[23–28]. Whenoccurs
the
quench fluorescence by electron or energy transfer [23–28]. When the quenching effect occurs
at a “trap site”
quenching effectwhere
occurstheat quencher MWCNT-COOH
a “trap site” associates
where the quencher with the polymer
MWCNT-COOH repeat
associates units,
with the
at a “trap site” where the quencher MWCNT-COOH associates with the polymer repeat units,
the quenching
polymer repeat effect
units, theofquenching
PMMA:MWCNT-COOH
effect of blends appears
PMMA:MWCNT-COOH in conjunction
blends appears in with the
conjunction
the quenching effect of PMMA:MWCNT-COOH blends appears in conjunction with the
strong
with theinteraction between
strong interaction PMMA
between and and
PMMA MWCNT-COOH
MWCNT-COOH with
withenergy
energymigration and/or
migration and/or
strong interaction between PMMA and MWCNT-COOH with energy migration and/or
delocalizationwithin
delocalization within MWCNT-COOH.
MWCNT-COOH.
delocalization within MWCNT-COOH.

Figure 7.7. TEMimages

imagesofof PMMA andand MWCNT-COOH. (a–c)(a–c)
TEMTEM patterns of pristine MWCNT-
Figure 7.TEM
Figure TEM images PMMA
of PMMA MWCNT-COOH.
and MWCNT-COOH. (a–c) patterns
TEM of pristine
patterns MWCNT-COOH
of pristine MWCNT-
COOH
with with
differentdifferent
ranges ranges
of of
vision; vision;
(d,e) (d)
TEM and (e)
patternsTEM
of patterns of PMMA:MWCNT-COOH
PMMA:MWCNT-COOH blends at blends
different
COOH with different ranges of vision; (d) and (e) TEM patterns of PMMA:MWCNT-COOH blends
at different
positions of positions
the same of
TEMthe same TEM grid.
at different positions of thegrid.
same TEM grid.

Figure 8. Characterization of MWCNT-COOH. (a) Raman spectrum of MWCNT-COOH; (b) TGA

Figure 8.8. Characterization
Figure Characterization of
of MWCNT-COOH.
MWCNT-COOH. (a) (a) Raman
Raman spectrum
spectrum of
of MWCNT-COOH;
MWCNT-COOH; (b)
(b) TGA
TGA
curves of MWCNT-COOH with different rising rates of temperature.
curves of MWCNT-COOH with different rising rates of temperature.
curves of MWCNT-COOH with different rising rates of temperature.
Nanomaterials 2018, 8, 114 9 of 11
Nanomaterials 2018, 8, 114 9 of 11

Figure 9.9. Fluorescence

Figure Fluorescence spectra
spectra of
of PMMA:MWCNT-COOH
PMMA:MWCNT-COOH blends blends in
in solutions
solutions with
with different
different mass
mass
fractions of MWCNT-COOH. Inset: photographs of the homogeneous solutions.
fractions of MWCNT-COOH. Inset: photographs of the homogeneous solutions.

Apart from TEM, Raman spectrum and TGA, the fluorescent quenching occurred when
Apart from TEM, Raman spectrum and TGA, the fluorescent quenching occurred when PMMA
PMMA noncovalently attached to the surface of CNTs. The resistive switching mechanism is
noncovalently attached to the surface of CNTs. The resistive switching mechanism is based on
based on MWCNT-COOH, and therefore can be closely linked with traps under a bias voltage.
MWCNT-COOH, and therefore can be closely linked with traps under a bias voltage. These traps
These traps have distinct energy levels that can be sequentially filled by increasing voltage,
have distinct energy levels that can be sequentially filled by increasing voltage, which contributes to
which contributes to tristable resistive switching behavior. The device behavior is associated
tristable resistive switching behavior. The device behavior is associated with charge carrier trapping
with charge carrier trapping and inter-CNT hopping by virtue of the effective distance
and inter-CNT hopping by virtue of the effective distance between neighboring CNTs or the CNT
between neighboring CNTs or the CNT content in the hybrid film [29]. With the CNT content
content in the hybrid film [29]. With the CNT content increasing from 1% to 3%, the distance between
increasing from 1% to 3%, the distance between isolated nanotubes was significantly
isolated nanotubes was significantly decreased. The diameter of individual CNTs is suitable for charge
decreased. The diameter of individual CNTs is suitable for charge hopping between
hopping between individual CNTs. Due to the strong electron-withdrawing ability of CNTs, a great
individual CNTs. Due to the strong electron-withdrawing ability of CNTs, a great deal of
deal of electron pathways can be formed throughout the entire nanocomposite. A larger number
electron pathways can be formed throughout the entire nanocomposite. A larger number of
of carrier pathways are responsible for the significant increment in the ON-state current and the
carrier pathways are responsible for the significant increment in the ON-state current and the
consequent growth in ION /IOFF once the threshold voltage was reached. A further increase in the
consequent growth in ION/IOFF once the threshold voltage was reached. A further increase in
CNT content up to 2% led to a simultaneous decrease in distance between isolated nanotubes. Charge
the CNT content up to 2% led to a simultaneous decrease in distance between isolated
carrier transport along the electron pathways by inter-CNT hopping becomes easier and occurs earlier
nanotubes. Charge carrier transport along the electron pathways by inter-CNT hopping
(intermediate state) than that in the binary WORM device, leading to less charge carriers being trapped
becomes easier and occurs earlier (intermediate state) than that in the binary WORM device,
prior to switching. Even though the applied voltage was removed, the charge largely remained trapped
leading to less charge carriers being trapped prior to switching. Even though the applied
since the deep trapping level prevented the detrapping process. ITO/PMMA:3%MWCNT-COOH/Ni
voltage was removed, the charge largely remained trapped since the deep trapping level
had a higher concentration of MWCNT-COOH, which made it easier to form pathways for charge
prevented the detrapping process. ITO/PMMA:3%MWCNT-COOH/Ni had a higher
hopping, initially resulting in the ON-state.
concentration of MWCNT-COOH, which made it easier to form pathways for charge hopping,
initially
4. resulting in the ON-state.
Conclusions
This work demonstrated a MWCNT-COOH-based resistive switching translating from bistable
4. Conclusions
into tristable behaviors through controllable charge trap CNTs. The one-dimensional carbon
This workalong
nanomaterial demonstrated a MWCNT-COOH-based
its axis, CNTs, mostly affected the resistive switching
electrical translating
behavior from bistable
of the hybrid films.
into tristable behaviors through controllable charge trap CNTs. The one-dimensional
The resistive switching mechanism based on MWCNT-COOH can be closely associated with traps carbon
nanomaterial
under along with
a bias voltage its axis, CNTs,
the fact thatmostly affected quenching
the fluorescent the electrical behavior
occurs. Theseofresults
the hybrid films.
may offer The
a new
resistive switching mechanism based on MWCNT-COOH can be closely associated with
strategy to heighten the performance of materials and stability of electronic devices by introducing traps under
a bias voltage
CNTs-based with the in
component fact that the
organic fluorescent
molecules quenching
for organic occurs.
multi-bit These
data results
storage may offer a new
devices.
strategy to heighten the performance of materials and stability of electronic devices by introducing
CNTs-based component
Acknowledgments: in organic
This work has beenmolecules
supportedforbyorganic
Project multi-bit data storage
of Heilongjiang devices.
Provincial Higher Education
Fundamental Research Funds for Basic Research (No. KJCXZD201702).
Acknowledgments:
Author This
Contributions: L.L.work has been
and D.W. supported
conceived by Project
and designed theof Heilongjiang
experiments; L.L.Provincial
performedHigher Education
the experiments;
L.L. and D.W. analyzed
Fundamental Research the
Fundsdata;
forL.L. wrote
Basic the paper.
Research (No. KJCXZD201702).
Conflicts of Interest: The
Author Contributions: authors
L.L. declare
and D.W. no conflict
conceived and of interest.the experiments; L.L. performed the experiments;
designed
L.L. and D.W. analyzed the data; L.L. wrote the paper.

Conflicts of Interest: The authors declare no conflict of interest.

Nanomaterials 2018, 8, 114 10 of 11

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