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Article history: The synthesis and novel fabrication of quantum dot layers has been performed by using electrohydrody-
Received 27 February 2014 namics atomization technique. The surface, optical and electrical properties of the fabricated lms have
Received in revised form 4 May 2014 been characterized by FE-SEM, TEM, spectroscopes and semiconductor device analyzer. The CdSe/ZnS
Accepted 7 May 2014
core/shell quantum dots have been synthesized and dispersed in toluene and DMSO as cosolvents. The
Available online 24 May 2014
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
Keywords:
layer for hybrid device has been optimized by changing the standoff distance of electrohydrodynamics
Electrohydrodynamics atomization
Conjugate polymers
atomization system. The exible hybrid device with optimized thickness of quantum dots showed red
Quantum dots light at 634 nm wavelength in visible range with 165 mA/cm2 current density and 2.2 lux of luminance
Hybrid light emitting diode at 15 V.
Flexible 2014 Elsevier B.V. All rights reserved.
1. Introduction polymer devices have advantages like easy fabrication, low cost,
lightweight, human friendly, sustainable raw materials, very thin,
Organic light emitting diodes (OLEDs) along with luminance large view angle, and fast response [3,4]. The solution-based
performance were rst reported in 1987 [1]. From there on a lot polymers make the fabrication process easy as compared to the
of research has been reported on OLEDs [2]. The conjugated 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
Corresponding author. Tel.: +82647543713; fax: +82647523174. layer, emissive layer is coated in which the holes and electrons
E-mail address: amm@jejunu.ac.kr (K.H. Choi). combine and emit photon. Electron transport layer is coated on
http://dx.doi.org/10.1016/j.cej.2014.05.067
1385-8947/ 2014 Elsevier B.V. All rights reserved.
326 M. Zubair et al. / Chemical Engineering Journal 253 (2014) 325331
top of emissive layer. Finally, the aluminum layer is thermally O/sq, cadmium oxide (CdO, 99.99%), zinc acetate (Zn(CH3COO)2
evaporated onto the electron transport layer as the reective 99.99%, powder), oleic acid(OA, 90%), trioctylphosphine (TOP,
cathode [6,7]. 90%), selenium (Se, 99.99%, powder), sulfur (S, 99.9%, powder), 1-
To enhance the emissive characteristics of OLEDs, quantum dots octadecene (90%), dodecanethiol (99%) and dimethyl sulfoxide
(QDs) have been used [810]. QDs are nanocrystal with excellent (DMSO, 99.9%) were purchased from Sigma Aldrich (South Korea).
emissive properties because of quantum connement effect [11]. PEDOT:PSS was purchased from Agfa Materials Japan. Acetone,
The narrow emission wavelength that is tunable throughout the chloroform, and isopropanol were purchased from Daejon
visible spectra, tunable band gap and solution process ability make Chemicals and Metal Co, Ltd, South Korea. All solvents were used
QDs excellent candidates in many application as emissive layers in as received.
OLEDs devices [12,13], composite materials [14], solar cells [15,16],
electroactive polymers [17] and biological imaging [11]. Since 2.2. Quantum dots ink synthesis
homogenous and uniform spray of QDs in large area is an essential
requirement in emissive devices [9], researchers have opted for CdSe/ZnS QDs were synthesized using the previously reported
dropping solution and then drying in oven [18], spin coating method with modication [34]. Briey, 2 mmol of CdO, 4 mmol
[19], spin coating with air-shear force [9] and transfer printing of Zn(CH3COO)2, 5 mL of OA were placed into 250 mL of three-neck
[20]. Still there is a need to adopt a fabrication technique that ask with vigorous stirring, and the temperature was raised to
can be deployed to produce thin lm for large area coverage. 150 C, followed by evacuation for 30 min. Then, 50 mL of
Electrohydrodynamics atomization (EHDA) is one of the easy, 1-octadecene was added, and then reactor was heated to 300 C
cost effective, and robust techniques for spraying which can be to form Cd(OA)2 and Zn(OA)2. At the elevated temperature,
applied for large area spray applications. EHDA is a single step 0.4 mL of 1 M TOPSe was rapidly injected into the reactor to pro-
spray process in which functional materials like polymer, nanopar- duce CdSe cores. After 1.5 min, 0.6 mL of dodecanethiol was added
ticles or quantum dots dissolved or dispersed in solvents are dropwise at rate of 1 mL/min, and the mixture was allowed to react
sprayed onto the substrate under the inuence of electric eld at at 300 C for 20 min under N2 atmosphere. To passivate QDs,
room temperature and atmospheric pressure [21]. A cone is formed 4 mmol of sulfur dissolved in 2 mL of TOP was added, and the reac-
at the exit of capillary by the surface tension of the solution work- tion proceeded for additional 10 min under N2 atmosphere. Then
ing against Maxwell stresses induced by the electric eld. The jet the mixture was cooled to room temperature to produce CdSe/
breaks into droplets and further disintegrates into smaller droplets ZnS core/shell QDs. For purication, chloroform and acetone were
by Coulomb forces and this continually ssion leads to micron added to the suspensions, followed by centrifugation at 7,000 rpm
sized droplets which are deposited on substrate and a uniform thin for 30 min and redispersion in toluene and DMSO cosolvent.
layer is achieved [22]. At different modes of EHDA phenomena can
be observed at different voltages. Researchers have used EHDA for 2.3. Device fabrication
spray purposes of organic and inorganic materials [2330].
Muhammad et al. [23] discussed characterization of Zinc Oxide The H-LED fabrication process and structure of device (ITO/PED-
(ZnO) sprayed by EHDA. Zirconium dioxide (ZrO2), Titanium OT:PSS/CdSe-ZnS QD/MEH-PPV/Al) is shown in Fig. 1. The ITO
dioxide (TiO2) graphene akes and graphene oxide were sprayed coated PET was initially cleaned by using acetone and then isopro-
by EHDA for memristor by Muhammad et al. [24], Maria et al. panol in bath sonicator for 15 min each. After cleaning, the ITO
[25], and Navaneethan et al. [26]. Organic polymers like poly coated PET was rinsed with deionized water and placed in oven
[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH- to dry for 15 min. The substrate was further cleaned to remove
PPV), Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) any organic contamination using ultraviolet (UV) treatment for
(PEDOT:PSS), poly(3-hexylthiophene) phenyl-C61-butyric acid 60 s. Aqueous solution of PEDOT:PSS was made by in-house proce-
methyl ester (P3HT:PCBM) and Poly[(9,9-di-n-octyluorenyl-2,7- dure using water and isopropanol which was explained clearly in
diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) solutions were our previous work [28]. The viscosity of aqueous PEDOT:PSS solu-
sprayed by EHDA by Muhammad et al. [27], Navaneethan et al. tion was 43.5 mPa.S. PEDOT:PSS was coated on ITO coated PET
[28,29], Choi et al. [31] and Maria et al. [30] respectively. Zhu using spin coating technique with spin coating speed of 1500 rpm
et al. and Wei et al. showed that the QD in ionic liquid aided in for 30 s. The thin layer was dried at 100 C for 30 min. CdSe/ZnS
the formation of polymer nanobers by electrospinning process quantum dots of 5 wt% were dispersed in toluene with dimethyl
[32,33]. sulfoxide (DMSO) as cosolvent. The viscosity of quantum dots
In this work, cadmium selenide/zinc sulde (CdSe/ZnS) core/ solution was 0.56 mPa.S. Quantum dots were sprayed using
shell quantum dots are sprayed by electrohydrodynamic atomiza- electrohydrodynamics atomization technique. After spray, the
tion process for the fabrication of exible hybrid OLED. The photo- device was dried in oven at 110 C for 1 h. Chloroform was used
luminance and transmission electron microscope (TEM) images are to make 0.5% MEH-PPV solution with viscosity of 4.76 mPa.S.
used to nd the size and emissive wavelength of QDs. A hybrid con- MEH-PPV was deposited on the device using spin coating technique
jugate polymer OLED is fabricated which has CdSe/ZnS QDs as emis- with 1500 rpm for 30 s. The thin lm was dried at 100 C for 30 min
sive layer. ITO is used as the transparent anode, PEDOT:PSS as hole in oven afterwards. The top electrode was made by thermally
transport layer, MEH-PPV as electron transport layer and aluminum evaporated aluminum at deposition pressure of 10 6 torr and depo-
as reective cathode. Electroluminance of the fabricated device is sition rate of 3 /s. The thickness of top electrode was 100 nm with
used to conrm the functionality of atomized emissive layer. active area of 0.8 0.8 cm2. After that, an ultraviolet (UV) exible
Current voltage (IV) characterization is performed to analyze the epoxy binder was used to encapsulate the device. Initially devices
electrical performance of hybrid-light emitting diode (H-LED). were fabricated on ITO coated glass substrate for the optimization
of spray process. Once the spray process was optimized, the ITO
2. Method coated glass substrate was replaced by ITO coated PET substrate.
MEH-PPV powder (average molecular weight 40,00070,000), The setup for EHDA is shown in Fig. 2. EHDA process was carried
ITO coated Polyethylene terephthalate (PET) with resistivity of 12 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.
2.5. Characterizations
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. 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.
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.
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