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Fabrication of CdSeZnS Quantum Dots Thin Film by Electrohydrodynamics Atomization Technique For Solution Based Flexible Hybrid OLED Application
Fabrication of CdSeZnS Quantum Dots Thin Film by Electrohydrodynamics Atomization Technique For Solution Based Flexible Hybrid OLED Application
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
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
326
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
The setup for EHDA is shown in Fig. 2. EHDA process was carried
out at room temperature (25 C & 50% humidity) and atmospheric
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
328
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.
329
Fig. 5. FE-SEM images of (a) PEDOT:PSS and (b) MEH-PPV thin layers.
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)
10
9
8
6
5
183
225
262
350
1156
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
330
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. 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.
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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