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Chemical Engineering Journal 253 (2014) 325331

Contents lists available at ScienceDirect

Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

Fabrication of CdSe/ZnS quantum dots thin lm by


electrohydrodynamics atomization technique for solution based exible
hybrid OLED application
Muhammad Zubair a, Maria Mustafa a, Kangtaek Lee b, Cheolsang Yoon b, Yang Hoi Doh c,
Kyung Hyun Choi a,
a

Department of Mechatronics Engineering, Jeju National University, 690-756, Republic of Korea


Department of Chemical and Biomolecular Engineering, Yonsei University, 120-749, Republic of Korea
c
Department of Electronics Engineering, Jeju National University, 690-756, Republic of Korea
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Synthesis of core/shell CdSe/ZnS

quantum dots.
 Spray of quantum dots by

electrohydrodynamics atomization
technique.
 Fabrication of hybrid organic light
emitting diode on PET substrate.
 Characterization of hybrid organic
light emitting diode.

a r t i c l e

i n f o

Article history:
Received 27 February 2014
Received in revised form 4 May 2014
Accepted 7 May 2014
Available online 24 May 2014
Keywords:
Electrohydrodynamics atomization
Conjugate polymers
Quantum dots
Hybrid light emitting diode
Flexible

a b s t r a c t
The synthesis and novel fabrication of quantum dot layers has been performed by using electrohydrodynamics atomization technique. The surface, optical and electrical properties of the fabricated lms have
been characterized by FE-SEM, TEM, spectroscopes and semiconductor device analyzer. The CdSe/ZnS
core/shell quantum dots have been synthesized and dispersed in toluene and DMSO as cosolvents. The
sprayed CdSe/ZnS quantum dots have been employed as emissive layer. The conjugate polymers of
PEDOT:PSS and MEH-PPV are used as the hole and electron transport layers. The thickness of emissive
layer for hybrid device has been optimized by changing the standoff distance of electrohydrodynamics
atomization system. The exible hybrid device with optimized thickness of quantum dots showed red
light at 634 nm wavelength in visible range with 165 mA/cm2 current density and 2.2 lux of luminance
at 15 V.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Organic light emitting diodes (OLEDs) along with luminance
performance were rst reported in 1987 [1]. From there on a lot
of research has been reported on OLEDs [2]. The conjugated

Corresponding author. Tel.: +82647543713; fax: +82647523174.


E-mail address: amm@jejunu.ac.kr (K.H. Choi).
http://dx.doi.org/10.1016/j.cej.2014.05.067
1385-8947/ 2014 Elsevier B.V. All rights reserved.

polymer devices have advantages like easy fabrication, low cost,


lightweight, human friendly, sustainable raw materials, very thin,
large view angle, and fast response [3,4]. The solution-based
polymers make the fabrication process easy as compared to the
inorganic conventional LEDs [5]. In OLEDs, usually Indium tin oxide
(ITO) coated glass is used as the transparent anode on which a hole
transport layer is casted by spin coating. On this hole transport
layer, emissive layer is coated in which the holes and electrons
combine and emit photon. Electron transport layer is coated on

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M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

top of emissive layer. Finally, the aluminum layer is thermally


evaporated onto the electron transport layer as the reective
cathode [6,7].
To enhance the emissive characteristics of OLEDs, quantum dots
(QDs) have been used [810]. QDs are nanocrystal with excellent
emissive properties because of quantum connement effect [11].
The narrow emission wavelength that is tunable throughout the
visible spectra, tunable band gap and solution process ability make
QDs excellent candidates in many application as emissive layers in
OLEDs devices [12,13], composite materials [14], solar cells [15,16],
electroactive polymers [17] and biological imaging [11]. Since
homogenous and uniform spray of QDs in large area is an essential
requirement in emissive devices [9], researchers have opted for
dropping solution and then drying in oven [18], spin coating
[19], spin coating with air-shear force [9] and transfer printing
[20]. Still there is a need to adopt a fabrication technique that
can be deployed to produce thin lm for large area coverage.
Electrohydrodynamics atomization (EHDA) is one of the easy,
cost effective, and robust techniques for spraying which can be
applied for large area spray applications. EHDA is a single step
spray process in which functional materials like polymer, nanoparticles or quantum dots dissolved or dispersed in solvents are
sprayed onto the substrate under the inuence of electric eld at
room temperature and atmospheric pressure [21]. A cone is formed
at the exit of capillary by the surface tension of the solution working against Maxwell stresses induced by the electric eld. The jet
breaks into droplets and further disintegrates into smaller droplets
by Coulomb forces and this continually ssion leads to micron
sized droplets which are deposited on substrate and a uniform thin
layer is achieved [22]. At different modes of EHDA phenomena can
be observed at different voltages. Researchers have used EHDA for
spray purposes of organic and inorganic materials [2330].
Muhammad et al. [23] discussed characterization of Zinc Oxide
(ZnO) sprayed by EHDA. Zirconium dioxide (ZrO2), Titanium
dioxide (TiO2) graphene akes and graphene oxide were sprayed
by EHDA for memristor by Muhammad et al. [24], Maria et al.
[25], and Navaneethan et al. [26]. Organic polymers like poly
[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV),
Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)
(PEDOT:PSS), poly(3-hexylthiophene) phenyl-C61-butyric acid
methyl ester (P3HT:PCBM) and Poly[(9,9-di-n-octyluorenyl-2,7diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) solutions were
sprayed by EHDA by Muhammad et al. [27], Navaneethan et al.
[28,29], Choi et al. [31] and Maria et al. [30] respectively. Zhu
et al. and Wei et al. showed that the QD in ionic liquid aided in
the formation of polymer nanobers by electrospinning process
[32,33].
In this work, cadmium selenide/zinc sulde (CdSe/ZnS) core/
shell quantum dots are sprayed by electrohydrodynamic atomization process for the fabrication of exible hybrid OLED. The photoluminance and transmission electron microscope (TEM) images are
used to nd the size and emissive wavelength of QDs. A hybrid conjugate polymer OLED is fabricated which has CdSe/ZnS QDs as emissive layer. ITO is used as the transparent anode, PEDOT:PSS as hole
transport layer, MEH-PPV as electron transport layer and aluminum
as reective cathode. Electroluminance of the fabricated device is
used to conrm the functionality of atomized emissive layer.
Current voltage (IV) characterization is performed to analyze the
electrical performance of hybrid-light emitting diode (H-LED).

O/sq, cadmium oxide (CdO, 99.99%), zinc acetate (Zn(CH3COO)2


99.99%, powder), oleic acid(OA, 90%), trioctylphosphine (TOP,
90%), selenium (Se, 99.99%, powder), sulfur (S, 99.9%, powder), 1octadecene (90%), dodecanethiol (99%) and dimethyl sulfoxide
(DMSO, 99.9%) were purchased from Sigma Aldrich (South Korea).
PEDOT:PSS was purchased from Agfa Materials Japan. Acetone,
chloroform, and isopropanol were purchased from Daejon
Chemicals and Metal Co, Ltd, South Korea. All solvents were used
as received.
2.2. Quantum dots ink synthesis
CdSe/ZnS QDs were synthesized using the previously reported
method with modication [34]. Briey, 2 mmol of CdO, 4 mmol
of Zn(CH3COO)2, 5 mL of OA were placed into 250 mL of three-neck
ask with vigorous stirring, and the temperature was raised to
150 C, followed by evacuation for 30 min. Then, 50 mL of
1-octadecene was added, and then reactor was heated to 300 C
to form Cd(OA)2 and Zn(OA)2. At the elevated temperature,
0.4 mL of 1 M TOPSe was rapidly injected into the reactor to produce CdSe cores. After 1.5 min, 0.6 mL of dodecanethiol was added
dropwise at rate of 1 mL/min, and the mixture was allowed to react
at 300 C for 20 min under N2 atmosphere. To passivate QDs,
4 mmol of sulfur dissolved in 2 mL of TOP was added, and the reaction proceeded for additional 10 min under N2 atmosphere. Then
the mixture was cooled to room temperature to produce CdSe/
ZnS core/shell QDs. For purication, chloroform and acetone were
added to the suspensions, followed by centrifugation at 7,000 rpm
for 30 min and redispersion in toluene and DMSO cosolvent.
2.3. Device fabrication

2. Method

The H-LED fabrication process and structure of device (ITO/PEDOT:PSS/CdSe-ZnS QD/MEH-PPV/Al) is shown in Fig. 1. The ITO
coated PET was initially cleaned by using acetone and then isopropanol in bath sonicator for 15 min each. After cleaning, the ITO
coated PET was rinsed with deionized water and placed in oven
to dry for 15 min. The substrate was further cleaned to remove
any organic contamination using ultraviolet (UV) treatment for
60 s. Aqueous solution of PEDOT:PSS was made by in-house procedure using water and isopropanol which was explained clearly in
our previous work [28]. The viscosity of aqueous PEDOT:PSS solution was 43.5 mPa.S. PEDOT:PSS was coated on ITO coated PET
using spin coating technique with spin coating speed of 1500 rpm
for 30 s. The thin layer was dried at 100 C for 30 min. CdSe/ZnS
quantum dots of 5 wt% were dispersed in toluene with dimethyl
sulfoxide (DMSO) as cosolvent. The viscosity of quantum dots
solution was 0.56 mPa.S. Quantum dots were sprayed using
electrohydrodynamics atomization technique. After spray, the
device was dried in oven at 110 C for 1 h. Chloroform was used
to make 0.5% MEH-PPV solution with viscosity of 4.76 mPa.S.
MEH-PPV was deposited on the device using spin coating technique
with 1500 rpm for 30 s. The thin lm was dried at 100 C for 30 min
in oven afterwards. The top electrode was made by thermally
evaporated aluminum at deposition pressure of 10 6 torr and deposition rate of 3 /s. The thickness of top electrode was 100 nm with
active area of 0.8  0.8 cm2. After that, an ultraviolet (UV) exible
epoxy binder was used to encapsulate the device. Initially devices
were fabricated on ITO coated glass substrate for the optimization
of spray process. Once the spray process was optimized, the ITO
coated glass substrate was replaced by ITO coated PET substrate.

2.1. Materials

2.4. Electrohydrodynamics atomization setup

MEH-PPV powder (average molecular weight 40,00070,000),


ITO coated Polyethylene terephthalate (PET) with resistivity of 12

The setup for EHDA is shown in Fig. 2. EHDA process was carried
out at room temperature (25 C & 50% humidity) and atmospheric

M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

327

Fig. 1. Device Structure and fabrication process of hybrid CdSe/ZnS QDs H-LED device.

(Motion Pro X) was used to observe the EHDA phenomena illuminated by a light source (Moritex MLET-A080W1LRD). The standoff
distance, which is the distance between the substrate and tip of
capillary, was changed from 10 mm to 5 mm to see the effect on
the thickness of QDs thin layer.
2.5. Characterizations

Fig. 2. Setup of Electrohydrodynamics Atomization Technique.

pressure. The in-house developed EHDA setup was consisted of a


metallic capillary, of internal diameter 110 lm, which was
attached to the nozzle adopter (NanoNC). This nozzle adopter
was connected to the syringe (Hamilton, Model 1001 GASTIGHT
syringe) placed in the infusion pump (Harward Apparatus, PHD
2000 infusion). This infusion pump controlled the ow rate of
the ink during spray process. The nozzle was attached to the
head-holder. Its motion along x, y and z axes was guided by three
linear motors controlled by NI motion controller (NI-PXI-7340)
was in placed in PXI (NI-PXI-8110). An interface board
(CW7764YS3) was used to setup communication and control of
limit switches. A program in National Instruments LabVIEWversion 8.6 was written, which allowed the movement the
head-holder in any pattern, which can be described by lines and
arcs. The metallic capillary was connected to a high voltage DC
source and the base on which the substrate was placed under
the metallic capillary was connected to ground. The DC signal
was generated by a function generator (Hewlett Packard 33120A)
and this signal was amplied using high power DC amplier (TREK
Model 610E). An oscilloscope (Hewlett Packard 54602B 150 MHz)
was attached to monitor the voltage. A high speed CCD camera

Surface morphologies of PEDOT:PSS and MEH-PPV lms were


analyzed by (FE-SEM) (JEOL JSM-7600F, Japan). This system was
operated at accelerating voltage of 5 kV. The QDs ink was analyzed
by transmission electron microscopy (TEM, JEOL JEM 2010). The
thickness of thin lm was measured by thin lm thickness measuring reectometer (K-MAC ST4000-DLX). Photoluminance (PL) of
QDs ink was observed by photoluminescence spectroscopy (Perkin
Elmer LS-55) with 365 nm excitation wavelength. The optical
properties were studied using ultra violet/visible spectrometer
(Shimadzu UV-3150) within visible color range 300800 nm. The
HOMO and LUMO values of the QDs were determined from the
cyclic voltammetry (CV) for which a three electrode electrochemical cell was used with a potentiostat (VSP, Bio-Logic). We used a
glassy carbon disk as a working electrode, a Pt wire as a counter
electrode, and a Ag/0.01 M AgNO3 + 0.1 M tetrabutylammonium
hexauorophosphate (TBAPF6) acetonitrile (Ag/Ag+) as a reference
electrode. The CV measurements were made from 2.0 V to 1.7 V
at a scan rate of 20 mV/s.
The electrical characterization of H-LED devices was performed
by semiconductor device analyzer (Agilent B1500A) with current
resolution of 1 fA. A probe station (MST8000C) was used to place
the samples during electrical performance analysis. The luminance
of the H-LED devices was measured by lux meter (Minolta LS-100).
The Commission International dEclairage (CIE) coordinates (x, y)
were also obtained by lux meter. The electroluminance (EL) of
devices was measured by calibrated spectrometer (Avantes
AvaSpec-ULS2048 StarLine Versatile Fiber-optic).
3. Results and discussion
Electrohydrodynamics atomization process consists of spraying
functional ink through capillary under the effects of electric eld.
When a functional ink was passed through a capillary at a ow
rate, in the absence of any electric eld drops of ink larger than
the capillary diameter were formed and dropped on substrate.
The voltage was increased gradually, keeping the standoff distance

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M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

at 10 mm and the ow rate of 100 ll/h. The size of drops falling


down on the substrate decrease with the increase of electric eld.
The stage when smaller droplets start detaching from meniscus is
known as the micro dripping which was observed at the voltage of
2.2 kV. Increase of voltage to 2.4 kV brought the meniscus in unstable cone jet. Here cone jet oscillated and ejected smaller droplet.
Further increase in voltage to 2.8 kV brought the stable cone jet
mode, which was used to spray. Further increase in voltage
brought the meniscus in multi-jet mode at the voltage of 3.0 kV.
Different modes of electrohydrodynamics phenomena are shown
in Fig. 3. As the ow rate affects the potential difference required
for the creation of stable cone jet mode [35], so an operating envelope was explored. At a certain ow rate, the voltage was increased
to observe the different modes of EHDA phenomena. The values of
voltage for corresponding EHDA modes were recoded. The operating envelope was plotted by repeating the experiment with different ow rates [36,37]. The operating envelope of CdSe/ZnS
quantum dots is shown in Fig. 4.
The surface morphology of thin layers of the fabricated
PEDOT:PSS and MEH-PPV onto ITO substrate were analyzed. The
FE-SEM images of thin lms of PEDOT:PSS and MEH-PPV are
shown in Fig. 5. The coated layers were non-porous, homogenous,
and densely packed. No defects like crakes or craters were
observed in thin lms. QDs were sprayed using EHDA technique
on PEDOT:PSS layer. Structural integrity of QDs was investigated
by TEM analysis. The TEM image of QDs is shown in Fig. 6 where
inset shows the lattice spacing of 0.4 nm. The average particle size
of QDs was about 6.58 nm.
To nd the optimized thickness to of the emissive layer for HLED device application, the standoff distance was varied form
10 mm to 5 mm. With the decrease of standoff distance, a decrease
in the spray area was observed; hence, the thickness of the
emissive layer was increased. The layer thickness change with
respect to change in standoff distance is presented in Table 1.
The normalized photoluminance intensity (PL) of QDs solution
and absorbance spectrum of QDs layer is shown in Fig. 7. The
QDs showed a single narrow peak at 634 nm. In visible light
spectrum, this wavelength lies in red color region. The absorbance
spectrum of CdSe/ZnS QDs layer corresponds to the reported
values in literature [38,39].
The electrical characterization of H-LED device was performed
to nd the performance of the device (ITO/PEDOT:PSS/QDs/MEHPPV/Al). The ITO acted as anode and was connected to positive
terminal of probe station while the aluminum was used as the

Fig. 4. Working Envelop of CdSe/ZnS Quantum Dots at different ow rates.

cathode and was connected to the negative terminal of probe station. The energies of materials dene the movements of holes and
electrons. The H-LED device energy diagram is shown in Fig. 8. The
highest occupied molecular orbital (HOMO), lowest unoccupied
molecular orbitals (LUMO) of ITO [40], PEDOT:PSS [41] and MEHPPV [42] were taken from the literature while the HOMO & LUMO
values of QDs were measured by cyclic voltammetry. The HOMO
and LUMO of QDs were found out to be
5.785 eV and
3.555 eV respectively with energy band gap of 2.23 eV. The PEDOT:PSS with high work function of 5.1 eV transports the holes
into QDs layer, where HOMO of QDs is 5.785 eV. The electrons
from the low work function of aluminum move into MEH-PPV,
which transport the electrons into the QDs. In the QDs layer the
holes combine with electrons to emit photons.
The current density with respect to voltage of H-LED devices on
glass substrates at different standoff distances and PET substrate at
6 mm standoff distance are shown in Fig. 9. Here it can be seen that
hybrid device (ITO/PEDOT:PSS/QDs/MEH-PPV/Al) shows non-ideal,
schottky diode behavior with hopping charge transport mechanism [43,44]. The current density of H-LED increased with the
decrease of standoff distance. The decrease of standoff distance
increased the lm thickness as area of spray was reduced. At the
standoff distance of 6 mm, highest current density was achieved

Fig. 3. EHDA phenomena where (a) shows the metallic capillary, (b) dripping mode, (c) micro-dripping mode, (d) unstable cone jet mode, (e) stable cone jet mode, (f) multi
jet cone mode.

M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

329

Fig. 5. FE-SEM images of (a) PEDOT:PSS and (b) MEH-PPV thin layers.

Fig. 7. Photoluminescence and absorbance spectrum of CdSe/ZnS Quantum dots


with inset showing quantum dots ink.

Fig. 6. TEM image of CdSe/ZnS quantum dots showing the size of QDs around 6.5
8 nm.

Table 1
Thickness of thin layer of QDs at different standoff distance.
Standoff Distance (mm)

Thickness of CdSe/ZnS QDs layer (nm)

10
9
8
6
5

183
225
262
350
1156

but further decreasing the standoff distance to 5 mm, wetting in


electrohydrodynamics atomization observed. In wetting phenomena, wet lm on substrate was observed instead of a semi-dry lm
after performing EHDA as droplet falls on substrate before they are
properly atomized into micron-sized particles. This wetting caused
the thin layer thickness to jump from 350 nm to 1156 nm and
hence a thick layer of QDs by wetting was achieved which showed
reduced current.
The exible device was xed in a lab made motorized cyclic
bending xture by which the device was tested at 5 mm radius
of curvature. The IV measurement was performed after number

Fig. 8. Energy Level Diagram of H-LED device.

of bending as shown in Fig. 10. The organic layers did not show
any degradation while lower current densities were attributed to
the brittle nature of ITO [45]. The recorded electroluminance of
hybrid device on glass and PET substrate with optimized distance
are shown in Fig. 11. The recorded emission or electroluminance
intensity of QDs H-LEDs was found at optimized distance was
the same wavelength as shown in the photoluminescence

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M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

Fig. 9. Log(I) V curves of hybrid devices with QD sprayed at different standoff


distances on glass and PET substrates with inset showing IV characterization.

Fig. 12. Luminance of the hybrid CdSe/ZnS QD device with respect to voltage is
shown on PET and glass substrate. The inset shows the H-LED at on-state.

Fig. 10. IV curves of exible H-LED after cyclic bending testing.

Fig. 13. Color coordinates on CIE chromaticity chart of H-LED at different voltages
on PET substrate are shown by black square while white cross represents the H-LED
devices on glass substrate.

Fig. 11. Electroluminescence of CdSe/ZnS quantum dots H-LED on glass and exible
substrate.

spectrum of QDs ink. This electroluminance intensity at the wavelength 634 nm showed that the achieved luminescence of the
device was by QDs layer and MEH-PPV acted as electron transport
layer and was not involved in any emission of light. The variation
luminance of H-LED with optimized 6 mm standoff distance with
voltage is shown in Fig. 12. The inset of the Fig. 12 shows the
glowing H-LED at on state on exible substrate. Maximum
luminescence of 2.4 lux was obtained at 15 V. The wavelength of
emission was at 634 nm, which lies in pure red region of visible
color range. The Commission International dEclairage (CIE) coordinates (x, y) were also obtained by lux meter are shown in Fig. 13 on
CIE chromaticity chart with black squares show the H-LED on PET
substrate while white cross represent the H-LED on glass
substrates at different voltages.

M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331

4. Conclusion
Using electrohydrodynamics atomization technique, the CdSe/
ZnS Quantum Dots have been successfully sprayed as an emissive
layer in exible hybrid organic light emitting diode application
with conjugate polymers as hole and electron transport layers.
Cadmium selenide/zinc sulde (CdSe/ZnS) core/shell quantum dots
have been synthesized with average size of 6.58 nm showing photoluminance peak at 634 nm wavelength. The operating envelop
for Quantum Dots spray has been established. Optimized standoff
distance for better device performance has been evaluated. The
surface morphology, optical and electrical characterization of thin
layer and H-LED device has been analyzed. With optimized thickness of 350 nm, the fabricated exible device show current density
of 165 mA/cm2 with maximum luminance of 2.2 lux at 15 V. The
results achieved for hybrid organic light-emitting diodes shows
the appealing applicability of EHDA techniques toward large area
optoelectronic devices.

Acknowledgements
This study is supported by the Technology Innovation Program
(No. 10041596, Development of core technology for TFT free active
matrix addressing color electronic paper with day and night usage)
funded by the Ministry of Knowledge Economy (MKE, Korea).

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