Materials Today Energy 20 (2021) 100704

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Materials Today Energy

journal homepage: www.journals.elsevier.com/materials-today-energy/

Fabrication of an oxide/metal/oxide structured electrode integrated

with antireflective film to enhance performance in flexible organic
light-emitting diodes
K.-J. Ko a, d, S.-R. Shin a, d, H.B. Lee a, E. Jeong b, Y.J. Yoo c, H.M. Kim c, Y.M. Song c, **,
J. Yun b, ***, J.-W. Kang a, *
a
Department of Flexible and Printable Electronics, LANL-CBNU Engineering Institute-Korea, Jeonbuk National University, Jeonju 54896, Republic of Korea
b
Surface Technology Division, Korea Institute of Materials Science, Changwon, Gyeongnam 51508, Republic of Korea
c
School of Electrical Engineering and Computer Science, Gwangju Institute of Science and Technology, Gwangju 61005, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Flexible organic light-emitting diodes (OLEDs) are used widely in optoelectronic devices, with possible
Received 27 December 2020 new applications, including foldable/rollable displays. Unique features of flexible OLEDs included high
Received in revised form brightness, low power consumption, and flexibility. The performance of a flexible OLED is frequently
14 February 2021
hindered by refractive index difference between the air and the flexible substrate medium, leading to
Accepted 4 March 2021
Available online 9 March 2021
inefficient light outcoupling. To address this issue, we developed a mechanically robust oxide/metal/
oxide (OMO) structured transparent conducting electrode (TCE), integrated with silica nanoparticles
ebased antireflective (AR) film, to improve the light extraction efficiency of flexible OLEDs. The AR-OMO
Keywords:
Light extraction
structures were prepared on polyethylene terephthalate substrates using a combination of plasma-
Silica nanoparticles enhanced chemical vapor deposition and magnetron sputtering. Our results show that an OLED device
Refractive index based on AR-OMO TCE exhibits higher luminance efficiency (LE) and total external quantum efficiency
OMO TCE (EQEtot) than devices based on pristine OMO or an indium tin oxide structure due to the presence of AR
Flexible OLED film that suppresses waveguided-mode light loss at the air-substrate interface. The champion AR-OMO-
based flexible OLED devices achieved an LE of 12.3 cd/A and an EQEtot of 5.0%. The AR-OMO device also
demonstrated outstanding mechanical flexibility, retaining 100% of its initial luminance up to a bending
radius of 6 mm.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction can be vapor-phase deposited on rigid or flexible substrates, is the

most popular TCE material in many flexible optoelectronic devices
Organic light-emitting diodes (OLEDs) have emerged as a next- because of its balanced optical transmittance-sheet resistance
generation display technology because of their high brightness, tradeoff. However, inherent brittleness, scarcity of indium, and
fuller viewing angle, wide color range, rapid refresh rates, and low non-vacuum-free manufacturing process have limited the appli-
power consumption. Furthermore, OLEDs have a simple design that cation of ITO in flexible OLED devices [3]. Various ITO-free alter-
is compatible with ultrathin, flexible, foldable, and transparent natives such as metal grid and nanowires (NWs) [2,4e9], carbon
displays [1,2]. The overall performance and flexibility of OLED de- nanotube (CNT) [10e12], graphene [13e15], conductive polymers
vices are governed by the optoelectronic properties of their trans- [16,17], and oxide/metal/oxide (OMO) structures [18e20] have
parent conductive electrodes (TCEs). Indium tin oxide (ITO), which evaluated as replacements for ITO in the fabrication flexible OLEDs.
Each candidate has notable weaknesses to be universally accepted
as the promising electrode candidate. For example, graphene re-
* Corresponding author. veals non-negligible disadvantages mainly because of the high
** Corresponding author. degree of technical difficulty associated with large-area and high-
*** Corresponding author. throughput fabrication [21], whereas CNTs and PEDOT:PSSs are
E-mail addresses: ymsong@gist.ac.kr (Y.M. Song), Jungheum@kims.re.kr (J. Yun),
often excluded from consideration for high-performance opto-
jwkang@jbnu.ac.kr (J.-W. Kang).
d
K.-J. K. and S.-R.S. made equal contribution to this article. electronic applications because of their inferior optical

https://doi.org/10.1016/j.mtener.2021.100704
2468-6069/© 2021 Elsevier Ltd. All rights reserved.
K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

transmittances [2]. The irregular, three-dimensional stacking suppression of optical reflection in the bottom side of the PET
structure of Ag NWs, which disrupts any sealing from an ambient substrate. All these factors are essential to both mitigating
environment, inevitably causes reliability issues owing to serious waveguided-mode light loss at the air/substrate interface and
oxidation and thermal degradation [22]. Contrastively, OMO efficient light outcoupling. The AR film was first prepared on PET
nanocomposite structures with an ultrathin noble metal film substrates using the PECVD to provide light extracting features to
sandwiched between oxide layers such as ITO/Ag/ITO [23], WO3/ the PET substrates without sacrificing optical transparency. The
Ag/WO3 [24], and ZnO/Ag/ZnO [19] are compatible with flexible OMO TCEs were fabricated by sequentially depositing ZnO, AgOx,
OLED application. The unique structural configuration of OMO and ZnO multilayers with different AgOx intermediate film thick-
electrodes successfully circumvents the aforementioned re- ness onto the AR/PET substrate through magnetron sputtering. The
strictions. The OMO electrodes ensure superior chemical and optoelectronic properties and device performance of the resulting
structural stabilities against corrosion and thermal loads along with AR/PET/OMO (AR-OMO) electrode were experimentally and theo-
their competitive optoelectrical properties. The mechanical flexi- retically evaluated.
bility and scalability of OMOs for continuous, large-area, high- Fascinatingly, the manipulation of the optical properties of the
throughput fabrication using roll-to-roll coaters add the merit of PET substrate with the simultaneous use of ZnO/AgOx/ZnO and AR
OMOs as promising ITO alternatives. configurations has led to an optical transmittance of 94.2% at
However, the actual practice of OMO electrodes is still limited 550 nm, which is far superior than any conventional ITO or OMO
mainly by the inferior optical transmittance compared with crys- electrode and is even higher than that of pristine PET substrate
talline ITO or Ag NWs. The serious reduction in the optical trans- without any coating. To the best of our knowledge, this is the
mittance is an inevitable consequence of the increased thickness of highest transmittance value ever reported for PET substrates coated
the metal layer in the OMO configuration, which are required to by OMO electrodes. The highly remarkable optoelectronic proper-
attain a competitive electrical conductivity. This optical loss is ties of the AR-OMO TCE also contributed to a significant improve-
inherent in metal layers because an increased thickness provides ment in the light extraction of the flexible OLEDs, enabling superior
more chances of photon scattering owing to the interaction with luminance efficiency (LE) and external quantum efficiency (EQE) of
free electrons in the metal layer. The single solution to resolve such the flexible AR-OMO-OLED compared with reference ITO-OLEDs
problem is the use of a decreased metal thickness in the OMO and pristine OMO-OLEDs. The bifunctional AR-OMO electrode-
configuration by accelerating the formation of a continuous layer. light extractor developed in this work is a low-cost and facile
Efforts focused on the synthesis of ultrathin intermediate Ag metal alternative that can replace ITO electrode, which degenerates easily
film on chemically heterogeneous oxides have been largely un- in mechanically flexible optoelectronic applications, such as flex-
successful owing to the lack of currently existing methodologies ible OLEDs.
and techniques [23]. Herein, we demonstrate the synthesis of a
completely continuous Ag intermediate layer at significantly 2. Experimental section
reduced thicknesses via atomic oxygen-mediated Ag growth to
produce OMO TCEs with a ZnO/AgOx/ZnO structure. This technique 2.1. Fabrication of the AR film
improved the likelihood of achieving simultaneously high optical
transmittance in the visible range and low electrical resistivity An SNA-based AR film was fabricated on PET (Panac Co.) sub-
[25e28]. Films composed of ZnO were selected as the top and strates 125 mm thick using a custom-built PECVD system at a
bottom oxide layers for the OMO structure because of their low capacitively coupled radio frequency (RF) discharge of 13.56 MHz,
cost, non-toxicity, high transmittance, and superior mechanical as we demonstrated previously [42e44]. First, the progressive
flexibility compared with ITO electrodes [19,29]. formation of nanoscopic polymer protrusions was induced on the
In an OLED device, a significant fraction of the emitted light is surface of the PET substrate through an argon plasma discharge
internally confined during the outcoupling process because of total process conducted at an RF power of 1.1 W/cm2 and a working
internal reflection at the air/substrate and substrate/TCE interfaces, pressure of 220 mTorr. The SNA (with an O:Si atomic ratio of
and only a small part of the total emitted light can escape from the 1.9e2.0) was deposited onto the PET substrate at the same power
light-emitting dielectric medium into the air [30]. This substrate- and working pressure using plasma polymerization of vaporized
trapped light loss reduces the eventual throughput and light yield hexamethyldisiloxane (HMDSO; Sigma-Aldrich, 98% purity) mixed
of the OLED device. According to multiple reports, outcoupling can with argon and O2 gases at a flow rate of HMDSO:O2:Ar ¼ 1.8: 10:
be improved by incorporating a light extracting nanophotonic 100 sccm. Both plasma treatment and silica deposition were con-
structures at the air/substrate and ITO/organic layer interface to ducted without intentional heating to avoid thermal damage to the
reduce the refractive index (n) difference and create additional light PET.
outcoupling routes [31]. For example, a micro-lens array (MLA)
[7,32,33], textured surface [34,35], and cylindrical geometry sub- 2.2. Fabrication of AR-OMO TCEs
strate [36] are widely reported to extract light confined in a sub-
strate. In addition, high refractive index substrates [37,38] and Transparent ZnO/AgOx/ZnO OMO TCEs were fabricated by
light-scattering layers [39e41] that facilitate the extraction of sequentially depositing ZnO, AgOx, and ZnO multilayers onto the
light trapped at TCEs and organic layers have also been studied. underside of the AR-coated PET substrates using magnetron sput-
In light of this, we fabricated an antireflection (AR) film tering (Flexlab System 100; A-Tech System Co. Ltd.) without
comprising silica nanoparticle arrays (SNAs) using a plasma- intentional heating [25]. The bottom (5 nm) and top (25 nm) ZnO
enhanced chemical vapor deposition (PECVD) technique on poly- films were deposited using a 4-inch ZnO target (99.999% pure ZnO;
ethylene terephthalate (PET) substrate to further enhance the op- Applied Science Co.) at an RF power of 200 W and a working
toelectronic properties of the OMO structure. An SNA is an ideal pressure of 3.0 mTorr in an argon atmosphere (flow rate ¼ 60 sccm)
candidate for AR film because it can scatter light, suppress reflec- without heating during and/or after sputtering. Using the same
tion from air/substrate interfaces, and enhance light transmission. sputtering system, embedded AgOx layers of different thicknesses
Furthermore, SNA has a refractive index of ~1.46, which is closer to (6, 8, and 10 nm) were deposited on the bottom ZnO films via a
air (n ¼ ~1.0) than the PET substrate (n ¼ ~1.58), and the geomet- direct current reactive sputtering process at a power of 50 W using
rical feature of the AR film implements a nearly complete a 4-inch silver target. Deposition of the AgOx layer was performed
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K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

at 3.0 mTorr in an Ar þ O2 atmosphere (Ar:O2 flow rate ¼ 45:4 2.5. Characterization of AR-OMO TCE-based flexible OLED
sccm). For the fabrication of the reference ITO TCE, an ITO film
160 nm thick was deposited onto the PET substrate using a 4-inch Surface morphology and three-dimensional (3D) imaging of the
In2O3 target doped with 10 wt% tin. AR/PET substrates were obtained from a field-emission scanning
electron microscope (FE-SEM; Hitachi S-4800). The sheet resistance
2.3. Fabrication of flexible OLEDs of the OMO TCEs was measured using a non-contact resistance
measurement instrument (Napson, EC-80P). The optical properties
Flexible OLEDs were fabricated on as-prepared (1) PET/ITO, (2) of the AR-OMO TCEs, including Ttotal and reflectance, were measured
PET/OMO, and (3) AR/PET/OMO TCE substrates. For fabrication of using ultraviolet (UV)evisible light spectrophotometry (Perkin
flexible OLEDs, an ethoxylated polyethyleneimine (PEIE) solution Elmer, Lambda 750). The optical constants of the AR-OMO TCEs were
(0.5 wt% in 2-methoxyethanol) was spin-coated onto the TCEs at measured using a spectroscopic ellipsometry. For device character-
5,000 rpm for 30 s to function as an interfacial charge transport ization, the current densityevoltageeluminance (J-V-L) character-
layer. The PEIE solution was filtered through a 0.45 mm polytetra- istics, EQE, electroluminescence (EL) spectra, and angle-resolved EL
fluoroethylene filter before spin-coating. Next, Super Yellow (PDY- intensity of the flexible OLEDs based on the different TCEs were
132, Merck) solution (5 mg/mL in toluene) was spin-coated onto measured using a source measure unit (Keithley 236) and a spec-
the TCE/PEIE substrates at 1,500 rpm for 30 s in an N2-filled troradiometer (Konta Minolta CS-2000) in ambient environment.
glovebox and postannealed at 70  C for 20 min to yield an emissive
layer 200 nm thick. The samples were then transferred to a high- 3. Results and discussions
vacuum (~106 Torr) chamber, where 10-nm-thick 1,4,5,8,9,11-
hexaazatriphenylenehexacarbonitrile (Lumtec) hole injection To enhance the performance of flexible OLEDs, it is necessary to
layer was thermally evaporated at a rate of 0.4e0.5 Å/s. To complete develop a bifunctional TCE-light extractor substrate to mitigate
the device fabrication, an aluminum (Al) top anode 100 nm thick light loss because of reflectance at the air/substrate interface and
was thermally evaporated onto the sample at an evaporation rate of navigate light out from the substrate. This can be realized by the
4e5 Å/s. The light-emission area of each OLED device was fixed at development of the AR-OMO TCE in this work. The fabrication of an
0.0525 cm2. AR-OMO TCE is initiated by the deposition of AR film on the PET
substrate. Instead of using nano-patterning by photolithography,
2.4. Theoretical simulation of AR-OMO TCEs we introduce a facile and maskless PECVD method for the direct
growth of SNA-based AR film on PET substrate. The growth process
Rigorous coupled-wave analysis (RCWA) and commercial soft- mainly consisted of two steps: (1) formation of a micro- or nano-
ware (DiffractMOD; RSoft Design Group, USA) were used to calcu- sized polymer protrusion array on a PET substrate via argon plasma
late the T and R of the AR-OMO TCEs. In the RCWA, the simulation treatment at 3 min, (2) deposition of silica nanoparticles on the
condition was set to the second diffraction order and a 0.2 nm grid polymeric protrusion array via PECVD. As shown in Fig. 1(a) and (b),
size to calculate the diffraction efficiency, which was enough to the growth of the SNA was initiated on top of the protrusion array,
numerically stabilize the results. Material dispersions and extinc- and the morphology of the protrusions array was determined by
tion coefficients were considered for obtaining exact outputs. For the duration of the argon plasma irradiation. Prolonged plasma
the navigation of light rays from the substrate to the air in an irradiation will cause coalescence of neighboring protrusions and
emission device, optical simulation based on the Monte Carlo consequently reduce the protrusions density. Because the
method was carried out using commercial software (Zemax morphology of a PET substrate is modified via argon plasma
OpticStudio; Radiant Zemax LLC, USA). treatment, an AR film can be considered the end product of the

Fig. 1. Schematic fabrication process of SNA-based AR film: (a) formation of nanoscopic polymer protrusions on PET substrate via plasma treatment and (b) deposition of SNA on
PET substrate via PECVD technique. (c) Schematic illustration and surface morphology of the as-prepared AR/PET film. Schematic illustration of (d) AR-OMO TCE and (e) flexible
yellow-OLED devices based on AR-OMO TCE. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

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K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

Fig. 2. (a) Ttotal spectra and (b) Rtotal spectra of ITO, OMO and AR-OMO TCEs prepared on PET substrates. (c) Measured/calculated refractive indices (n) of the AR films with different
SNA densities.

etching, migration, redeposition, and recombination of the polymer the top and bottom ZnO electrodes and AgOx interlayer in the OMO
substrate [42]. The top-view and cross-sectional FE-SEM images in structure were also measured and presented in Fig. S3.
Fig. 1(c) depict that the SNA in AR film has an average diameter of Furthermore, the optical properties of the pristine OMO and AR-
~78 nm, and the AR film has an effective thickness of ~180 nm. OMO TCEs were theoretically calculated, and the simulated Ttotal
Additional top-view FE-SEM images of the pristine PET substrate and Rtotal spectra of the pristine OMO and AR-OMO TCEs are pre-
and AR/PET film can be found in Fig. S1, Supporting Information. sented in Fig. S4. The simulated T550nm and the Tavg (400e700 nm)
After the preparation of AR film, OMO (ZnO/AgOx/ZnO) TCE were of the AR-OMO TCE were recorded at ~75% and ~68%, respectively.
deposited on the opposite side of the PET substrate via PECVD. The Pristine OMO TCE (without AR film) exhibited lower simulated
OMO TCE was composed of an AgOx layer sandwiched between top T550nm (~69%) and Tavg (400e700 nm; ~63%). The simulated R550 nm
and bottom ZnO films, as shown in Fig. 1(d). The intermediate AgOx and Ravg (400e700 nm) of the AR-OMO TCE were also lower than
layer enabled a remarkable degree of enhancement of the opto- that of pristine OMO TCE. The measured and simulated optical
electronic properties of the OMO TCE by minimizing the absorption parameters for the pristine OMO and AR-OMO TCEs are summa-
of incident light and carrier scattering [25]. Flexible yellow-OLEDs rized in Table 1. In relation to this, Fig. 2(c) suggests that the
were then fabricated on the AR-OMO TCE, as can be seen in Fig. 1(e). refractive indices (n) of the AR film, measured by dividing it into
We first investigated the optical properties of the as-prepared three mediums with different densities, became higher as the
AR-OMO TCE and compared its performance to pristine OMO density of the silica nanoparticles (SNP) increased. Because of this
and ITO (reference) TCEs. Fig. 2(a) presents the total transmittance gradual effective change in n, the measured/simulated Ttotal of the
(Ttotal) of ITO, OMO, and AR-OMO TCEs deposited on PET substrates AR-OMO substrate increased marginally with the use of AR film
in the UVevisible spectral range of 400e800 nm. The recorded compared with the pristine counterpart. Both experimental and
Ttotal spectra of the ITO, OMO, and AR-OMO TCEs took into account simulated results have coherently confirmed the beneficial use of
the background transmittance of PET substrate (Ttotal > 90% at SNA-based AR film in enhancing the optical properties of the AR-
400e800 nm). At a wavelength (l) of 550 nm, the PET/OMO OMO TCE.
sample exhibited a T550 nm of ~90%, which was much higher than To verify the efficacy of ITO, OMO, and AR-OMO TCE substrates in
the PET/ITO reference sample T550 nm of ~82%. Further incorpora- flexible OLED applications, we fabricated ITO-OLED, OMO-OLED, and
tion of AR film enabled an AR/PET/OMO sample to achieve a T550 nm AR-OMO-OLED devices and evaluated their emission characteristics.
of ~94%, which was 4% higher than that of the PET/OMO analog. Detailed device configuration of the flexible OLED device is illus-
Evidently, the simultaneous use of OMO electrode and AR con- trated schematically in Fig. 3(a). The thickness of the AgOx interlayer
figurations has enabled the AR-OMO TCE to achieve an optical in OMO-OLED and AR-OMO-OLED was prefixed at 8 nm. Preliminary
transmittance that is far superior than the ITO or pristine OMO results obtained during the optimization of AgOx thickness in OMO
counterparts and is even higher than that of pristine PET substrate structures are presented in Fig. S5 and Table S2. Fig. 3(b) depicts the
without any coating. To the best of our knowledge, this is the typical the current densityevoltageeluminance (J-V-L) characteris-
highest transmittance value ever reported for PET substrates tics curves of as-fabricated flexible OLEDs based on different TCEs.
coated with OMO electrodes reported thus far, as presented in There are no significant changes observed in the electrical charac-
Table S1. In the case of AR/PET/OMO sample, the increase of in- teristics of the ITO-OLED and OMO-OLED devices. Dark J-V charac-
termediate AgOx layer thickness (from 6 to 10 nm) in the OMO teristic curves in Fig. S6 reveal that the OMO-OLED and AR-OMO-
structure resulted in a gradual decline of Ttotal, particularly in the l OLED exhibited lower leakage current than the ITO-OLED device.
region of >550 nm region, as can be seen in Fig. S2(a). The total Lower leakage current indicates more efficient charge injection and
reflectance (Rtotal) values of the ITO, OMO, and AR-OMO deposited suppressed non-radiative charge recombination in the OLED device
on PET substrates are provided in Fig. 2(b). The PET/OMO (without
AR film) sample exhibited ~5% lower Rtotal at a wavelength of
Table 1
550 nm (R550 nm) compared with the PET/ITO sample. The presence
Optical properties of ITO-, OMO-, and AR-OMO-coated PET substrates.
of AR film further quenched the R550 nm of the OMO structure to
~1.2%. The reduced reflectance to ambient light in the OMO TCE Substrate Rsheet (U/sq.) T550 nm (%) Tavg (%) R550 nm (%) Ravg (%)
proved helpful in improving the image contrast of the penultimate Exp. Sim. Exp. Sim. Exp. Sim. Exp. Sim.
OLED device. With increasing AgOx layer thickness from 6 to PET e 90.9 e 90.8 e 8.7 e 8.8 e
10 nm, there is a corresponding decrease in the R550 nm value of PET/ITO 32.4 81.7 e 77.9 e 8.8 e 13.7 e
the AR/PET/OMO sample (Fig. S2(b)), indicating the superior PET/OMO 11.2 90.1 69.1 86.1 62.9 5.4 13.3 8.0 18.0
antireflection properties of the intermediate AgOx layer in the AR/PET/OMO 11.2 94.2 75.1 89.5 68.4 1.2 5.7 4.4 11.1
OMO structure. The refractive index and extinction coefficient of Exp, experimental; Sim, simulated.

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K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

Fig. 3. (a) Schematic device structure of a flexible OLED device using different TCE substrates. (b) J-V-L characteristic curves, (c) LE luminance plots, (d) EQE luminance plots, (e) EL
spectra measured at 20 mA/cm2, and (f) normalized luminance as a function of r of the flexible ITO-OLED, OMO-OLED, and AR-OMO-OLED devices.

based on the OMO TCEs [45]. Only a minor difference was evident increasingly smaller r. At r ¼ 4 mm, the OMO-OLED and AR-OMO-
between the electrical characteristic of OMO-OLED and AR-OMO- OLED retained as much as ~80% of their original luminance,
OLED films. Because the AR film is designed in such a way that it whereas the ITO-OLED suffered 90% loss of luminance. Further-
is attached externally to the OLED structure, it had no adverse effect more, the bending cycle test results (Fig. S7) show the AR-OMO-
on the device configuration or electrical conductivity of OLED device. OLED devices retained >80% of the initial luminance after being
However, the introduction of AR film greatly improved the lumi- repeatedly bent for 900 cycles at r of 6 mm, confirming that the
nance of the OLEDs at the same driving voltage, implying that the AR OMO-structured TCE exhibited a superior mechanical flexibility
film was efficiently extracted internally confined photons in the than the common ITO TCE, and the integration of AR film had no
form of a substrate waveguide mode, improving the light out- adverse effect on the flexibility of the OLED device. The rapid
coupling efficiency [46]. Maximum luminance (Lmax) values for the deterioration in the ITO-OLED caused the brittle nature of the ITO
ITO-OLED, OMO-OLED, and AR-OMO-OLED were recorded at ~8,300, TCE, which is known to exhibit low tolerance toward mechanical
~8,150, and ~9,400 cd/m2, respectively. The corresponding LE of the stress and cracks easily [47]. The bending result directly confirmed
AR-OMO-OLED was much higher than those of the ITO-OLED and that the OMO-structured TCE exhibited a superior mechanical
OMO-OLED devices, as shown in Fig. 3(c). At 5,000 cd/m2, the LE flexibility than the common ITO TCE, and the integration of AR film
values for the ITO-OLED, OMO-OLED, and AR-OMO-OLED devices had no adverse effect on the flexibility of the OLED device.
were 8.8, 8.9, and 12.2 cd/A, respectively. Because of the presence of The total EQE (EQEtot) of the flexible OLED devices based on ITO,
AR film, the AR-OMO-OLED achieved a maximum LE (LEmax) of OMO, and AR-OMO TCEs was measured with an integrating sphere
12.3 cd/A, which was much higher than that of the ITO-OLED (9.2 cd/ using a previously described method [6,22], with the results shown
A) and OMO-OLED (9.6 cd/A) devices. As a result, the EQE of AR- in Fig. 4(a). Unlike the calculation of normal EQE, which is based on
OMO-OLED reached 4.8%, which was much higher than that of the the collection of light power from a direction normal to the device,
ITO-OLED (3.7%) and OMO-OLED (3.8%) counterparts, as shown in the calculation of EQEtot (using an integrating sphere) is based on
Fig. 3(d). Fig. 3(e) provides the EL spectra of the OLEDs based on the the collection of all scattered light power in the surroundings [7].
ITO, OMO, and AR-OMO TCEs at a current density of 20 mA/cm2. The The results reveal that the use of an external AR film produced
EL intensity of the AR-OMO-OLED was apparently higher than the significantly higher values for EQEtot (~5.0%) in the AR-OMO-OLED
ITO-OLED and OMO-OLED because of the presence of an external AR (EQEtot ~5.0%), recording 1.31 and 1.25 enhancement ratios rela-
film that efficiently extracted the light trapped in the substrate tive to the EQE of ITO-OLED (~3.8%) and OMO-OLED (~4.0%),
waveguide mode. respectively. The device parameters of the flexible OLEDs based on
A bending stability test was conducted to evaluate the me- the different TCEs, including turn-on voltage (Von), maximum
chanical flexibility and robustness of the ITO-OLEDs, OMO-OLEDs, luminance (Lmax), LE, EQE, and EQEtot are summarized in Table 2.
and AR-OMO-OLEDs. The bending stability test was conducted by To further understand and illustrate the roles of AR film together
bending the devices for five cycles at reducing bending radius (r) with OMO structure in the light outcoupling mechanism of an OLED
from 10 mm to 1 mm. As presented in Fig. 3(f), when r was reduced device, a full trans-scale optical simulation was conducted using
from 10 to 6 mm, only negligible degradation occurred in the OpticStudio (Zemax llc.), a commercial 3D optical analysis software
normalized luminance (L/L0) of both the OMO-OLED and AR-OMO- based on ray tracing and Monte Carlo methods [36]. The ray-tracing
OLED, despite the significant mechanical strain exerted on them. simulation results provided light extraction efficiency, outcoupled
Contrarily, the L/L0 of the ITO-OLED deteriorated rapidly when r was power, and angular patterns of the flexible OMO-OLED devices
less than 10 mm, and the disparity between the L/L0 of the ITO- (without AR film) and AR-OMO-OLED devices (with AR film). The
OLED and AR-OMO-OLED became increasingly larger with amount of light ultimately emitted from the substrate to the air was

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K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

Fig. 4. (a) EQEtot-J plots of different types of flexible OLEDs measured with an integrating sphere. Ray-tracing simulation outcome: (b) A comparison between the light extraction
ratio of flexible OMO-OLED and AR-OMO-OLED structures. (c) Visualization of light navigation pathways for OMO and AR-OMO substrate structure. (d) Radiant intensity contour
plots of flexible OMO-OLED and AR-OMO-OLED.

Table 2 exhibited the highest emission at large viewing angle, suggesting

Summary of flexible OLED performance. that AR film was effective at suppressing surface reflection light loss
Devices Von (V) Lmax (cd/m2) LEmax (cd/A) EQE (%) EQEtot (%)
and optical microcavity effects [48,49]. In the presence of AR film,
the flexible OLED device generated more side-direction emissions
ITO-OLED 2.6 ± 0.1 8,300 ± 350 9.2 ± 0.4 3.7 ± 0.4 3.8 ± 0.3
in the emission intensity distribution pattern. The use of AR film
OMO-OLED 2.7 ± 0.1 8,150 ± 450 9.6 ± 0.2 3.8 ± 0.3 4.0 ± 0.5
AR-OMO-OLED 2.8 ± 0.1 9,400 ± 520 12.3 ± 0.5 4.8 ± 0.4 5.0 ± 0.4 can therefore mitigate emission intensity loss in OLEDs with an
increase in viewing angles. The normalized EL intensity in Fig. 5(b)
further shows that there is only negligible wavelength shift in the
calculated by tracing a total of 10 M rays at wavelength (550 nm). As EL of the AR-OMO-OLED with increasing viewing angle. The full
revealed by the simulation results in Fig. 4(b), the light extraction width at half maximum (FWHM) of the EL spectra was noticeably
ratio for an OLED device was improved after applying AR film. reduced with increasing viewing angle, implying that the AR-OMO
Comparatively, the light extraction ratio for the AR-OMO-OLED was bifunctional TCE-light extractor helped improve the emission uni-
~1.08 times greater than that of the OMO-OLED. Fig. 4(c) visualizes formity of the flexible OLEDs at larger viewing angles.
the light outcoupling process at the air/substrate interface in the
OMO-OLED and AR-OMO-OLED. The simulation results in a dra-
matic surge in the light navigation pathway of the AR-OMO- 4. Conclusion
OLED because of the suppression of total internal reflection at the
air/substrate interface by the AR film. Moreover, the contour plots We successfully prepared a bifunctional AR-OMO TCElight
in Fig. 4(d) reflect the relatively high radiant intensity of the AR- extractor layer for a flexible OLED application. Optical properties
OMO-OELD compared with that of the OMO-OLED. The trends of of AR-OMO TCEs were superior to those of pristine OMO and ITO
the simulated results generally agree with the trends from the counterparts, achieving a T550 nm of ~94% and a reflectance as low as
experimental results, and both experimental and simulated results ~1.2%. In the presence of SNA-based AR film, the n difference be-
show that the use of AR film is the main driving factor behind the tween the air and the PET substrate was reduced, thereby reducing
improvement in emission properties (EQE, EQEtot, and light the substrate waveguided-mode light loss and enhancing the light
extraction ratio) of flexible OLED devices. outcoupling from flexible OLED device. This resulted in superior
We then evaluated the device performance of a flexible OLED light-emitting performance in flexible OLED devices. The champion
device in terms of Lambertian emission distribution in a viewing AR-OMO-OLED device achieved an LE of 12.3 cd/A and an EQEtot of
angle range of 70 to 70 . The emission intensity distributions for 5.0%, exceeded the performance of a reference ITO-OLED with a LE
all of the devices were obtained at a constant luminance of 100 cd/ of 9.2 cd/A and an EQEtot of 3.8%. Furthermore, the flexible OMO-
m2, with the angular EL profiles depicted in Fig. 5(a). The ITO-OLED OLED and AR-OMO-OLED also demonstrated much greater me-
device demonstrated poor performance, and Lambertian emission chanical flexibility compared with ITO counterpart, retaining >95%
was not achieved. However, both OMO-OLED and AR-OMO-OLED of their initial luminance under intense bending conditions
devices produced Lambertian emission with higher EL intensity at (r ¼ 6 mm). The novel design of AR-OMO TCElight extractor
larger viewing angles. Among the three devices, the AR-OMO-OLED demonstrated herein provides a method to boost the light
6
K.-J. Ko, S.-R. Shin, H.B. Lee et al. Materials Today Energy 20 (2021) 100704

Fig. 5. (a) Angular EL profile of flexible OLEDs based on different TCE structures. (b) Normalized EL spectra of flexible AR-OMO-OLED at different viewing angles.

extraction efficiency of flexible OLEDs without modifying the active textile lighting, Adv. Mater. Technol. 5 (2020) 1e8, https://doi.org/10.1002/
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Declaration of competing interest
10.1002/aenm.201300474.
[10] D. Zhang, K. Ryu, X. Liu, E. Polikarpov, J. Ly, M.E. Tompson, C. Zhou, Trans-
The authors declare that they have no known competing parent, conductive, and flexible carbon nanotube films and their application
in organic light-emitting diodes, Nano Lett. 6 (2006) 1880e1886, https://
financial interests or personal relationships that could have
doi.org/10.1021/nl0608543.
appeared to influence the work reported in this paper. [11] J. Li, L. Hu, L. Wang, Y. Zhou, G. Grüner, T.J. Marks, Organic light-emitting
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This research was financially supported by the Creative Mate- b603821m.
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Science Research Program (2021R1A2C2004206, efficient graphene-based flexible organic light-emitting diodes, Nat. Commun.
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National Research Foundation of Korea (NRF) funded by the Min- Extremely efficient flexible organic light-emitting diodes with modified gra-
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