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Article
Fabrication of Flexible White Light Emitting Diodes from
Photoluminescent Polymer Materials with Excellent Color Quality
Huang Yu Lin, Chin-Wei Sher, Chih-Hao Lin, Hsien-Hao Tu, Xin Yin Chen, Yi-
Chun Lai, Chien-Chung Lin, Huang-Ming Philip Chen, Peichen Yu, Hsin-
Fei Meng, Gou-Chung Chi, Keiji Honjo, Teng-Ming Chen, and Hao-Chung Kuo
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b03386 • Publication Date (Web): 11 Sep 2017
Downloaded from http://pubs.acs.org on September 13, 2017

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Fabrication of Flexible White Light Emitting Diodes
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7 from Photoluminescent Polymer Materials with
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Excellent Color Quality
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Huang-Yu Lin,¶ Chin-Wei Sher, ¶, # Chih-Hao Lin, ¶ Hsien-Hao Tu, ¶ Xin Yin Chen, ¶ Yi-Chun Lai, ¶
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15 Chien-Chung Lin,∥,* Huang-Ming Chen, ¶ Peichen Yu, ¶ Hsin-Fei Meng, † Gou-Chung Chi, ¶ Keiji Honjo,
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18 ‡
Teng-Ming Chen, § and Hao-Chung Kuo¶,*
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21 ¶
22 Department of Photonics and Institute of Electro-Optical Engineering, National Chiao Tung
23 University, Hsinchu, Taiwan
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#
25 Hong Kong University of Science and Technology, Hong Kong
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§
27 Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan
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∥
29 Institute of Photonic System, National Chiao Tung University, Tainan, Taiwan
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31 †
Institute of Physics, National Chiao Tung University, Hsinchu, Taiwan
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33 ‡
ICE Cube Center WOW 3DI Laboratory, Rm.307 Bldg. J3, 4259, Nagatsuta-cho, Midori-ku Yokohama,
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Kanagawa, Japan
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36 *
37 To whom correspondence should be addressed: (H.C. Kuo) hckuo@faculty.nctu.edu.tw; (C.C. Lin)
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39 chienchunglin@faculty.nctu.edu.tw.
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42 KEYWORDS: Light emitting diode; Polyfluorene; Quantum dots; Flexible device, Color rendering
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44 index
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47 BRIEFS: A simple approach for demonstrating flexible LEDs with excellent color quality and
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49 reliability.
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55 ABSTRACT
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57 This study developed flexible light-emitting diodes (LEDs) with warm white and neutral white light.
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59 A simple ultraviolet flip-chip sticking process was adopted for the pumping source and combined with
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polymer and quantum dot (QD) films technology to yield white light. The polymer-blended flexible
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3 LEDs exhibited higher luminous efficiency than the QD-blended flexible LEDs. Moreover, the
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5 polymer-blended LEDs achieved excellent color rendering index values (Ra = 96 and R9 = 96), with
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high reliability, demonstrating high suitability for special applications like accent, down or retrofit lights
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10 in the future. In the places such as museum, kitchen or surgery room, its high R9 and high CRI
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12 characteristics can provide high quality of services.
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17 INTRODUCTION
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19 Recently, white light emitting diodes (LEDs) have received considerable attention because of their
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22 high luminousity, high light density, stable reliability, and energy efficiency.1,2 For daily life
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24 requirements related to lighting or displays, conventional high-efficiency white LEDs with gallium
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26 nitride blue chip and yttrium aluminium garnet phosphor have been developed.3,4 To improve LEDs and
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29 extend their application range, developing high-quality white LEDs with special features is crucial. To
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31 further extend the application of white LEDs, high color quality and bending characteristics are critical
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criteria.
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36 Organic LEDs (OLEDs) offer the highest potential for fabricating flexible lighting devices. They
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38 have received considerable attention because of their excellent color quality and thinness and are thus
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41 used in artistic lighting and displays. Because of the increasing prevalence of wearable technologies,
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43 numerous researchers have developed high-quality flexible OLEDs and inorganic LEDs. Many research
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45 groups have focused on developing electrode designs for flexible substrates, such as nitride nanowires,
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48 reduced graphene oxide, and cellulose/epoxy substrates,5–7 as well as improving the mechanical strength
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50 of InGaN/GaN epitaxial LEDs subjected to external bending strain.8 Rogers et al. used flexible LED
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52 technology integrated with a specialized epitaxial semiconductor layer to create or transfer-print micro-
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55 LED chips and systematically analyzed interconnected components in related nanoscale systems.9–13
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57 The main factors related to flexible LEDs that require consideration include luminous efficiency,
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bending curvature, and reliability,14,15 as well as color quality parameters such as the color rendering
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index (CRI) and CRI R9. Recently developed OLEDs can be used as flexible devices and provide high-
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3 CRI lighting. However, according to the results of a benchmark image test (Supporting Information, Fig.
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5 S1), achieving a high CRI results in a degraded luminous efficiency.16–29 When they performed the same
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benchmark test, Zhou et al. achieved a high CRI (96) but a low efficiency (5.5 lm/W).22 Su et al.
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10 developed an OLED with high luminous efficiency (44 lm/W) but low CRI (68).16 Therefore, achieving
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12 a balance between CRI and luminous efficiency in OLEDs is challenging.
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In this study, we demonstrate flexible white LEDs that were developed using two types of flexible
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17 film; one was fabricated using quantum dots (QDs), and the other was fabricated using polymers. QDs
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19 are well-known lighting materials because of their high quantum yield, size-dependent tunable bandgap,
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22 and narrow emission linewidth. Different reported designs have placed QDs in standard LED
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24 packages.30-32 Currently, polymer LEDs (PLEDs) are attracting great interest because of their high
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26 emission efficiency and easy solution process, which make them suitable for numerous specific lighting
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29 applications such as interior design, cars, and displays. Much research has investigated polymer films
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31 for many applications, Peter J. Skabara’s group demonstrated the excellent hybrid inorganic/organic
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white light LEDs CHDV as an encapsulating, UV-curable matrix, a dilute solution (1% w/v) of organic
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36 converter material combined with a blue chip. In this study, we selected polyfluorene (PFO) to
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38 fabricate films for our research.34-37 The polyfluorene (PFO) polymer exhibits not only the optimal
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41 luminous efficiency but also the excellent color render property, and was the popular materials as the
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43 active layer for OLED. PFO group polymers were with the broadband emission wavelength and can be
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45 control the band-gap by the ligand doping to modulate emission wavelength.38-39 As the PFO with the
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48 excellent optical property, several researches have reported the use of the hybrid polymer/QD LEDs to
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50 obtain the excellent optical characteristic.40-42 In the past, our group have been investigated the hybrid
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52 QD/polymer structure to optimized white LEDs, by discussion, PFO was the good candidate for w-LED
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55 and would be used in this study.43-44 Other recognized photoluminescent polymers, such as F8BT, have
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57 similar emission wavelengths to those required in this study. However, the quantum yield of F8BT is
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approximately 50%, which is lower than that of PFO,45 and F8BT is poorly excited at the wavelength of
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400 nm,46 thus making it unsuitable for the present study. When the spectrum, color quality, and
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3 quantum yield were all taken into consideration, PFO was selected for use in the fabrication of a flexible
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5 LED that would be compared with QD samples. This study used a QD film consisting of red, green, and
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blue CdSe/ZnS QDs and a polymer film comprising PFO, PFO-GreenB, and PFO-mono
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10 dibenzothiophene (DBT) to develop warm white and neutral white flexible LEDs, respectively. The
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12 results demonstrate that using polymers in flexible LEDs yields LEDs with excellent color quality and
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efficiency.
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19 EXPERIMENTAL METHODS
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22 Flexible substrate’s electrode design: Polyimide (PI) is a favorable candidate for the development of
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24 reliable flexible substrates. We defined the area of the electrode through wet etching and
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26 photolithography, and then coated it with 30 µm of bonding adhesive to facilitate the adhesion of the
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29 metal electrode to the substrate. Next, a 14.2 g copper stripe with a thickness of approximately 30 µm
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31 was coated onto the substrate using an e-gun. Following the anisotropic conductive adhesive bonding
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approach, the gap between the bonded anode and cathode pads was set to approximately 100 × 1500
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36 µm2 (L × W).47 The flexible design and top view of the chip bonding is displayed in Supporting
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38 Information Figure S2.
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41 UV flip-chip bonding on the flexible substrate: First, we prepared UV flip-chips (Lextar Electronics
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43 Corporation, Taiwan) with a wavelength of 400 nm and chip size of approximately 1143 × 1143 µm.
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45 Next, we bonded the UV flip-chips onto the electrode layout by using a silicone-based anisotropic
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48 conductive adhesive (Dexerials Corporation) at a temperature of 230 °C and pressure of 22.5 kg for 180
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50 s. Finally, the flexible LED was molded using 1-mm-thick polydimethylsiloxane (PDMS). After thermal
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52 treatment and pressurizing, conduction was induced by the metal particles between the bonding and
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55 electrode pads. The anisotropic conductive adhesive filled the gap between the two pads but did not
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57 enable conduction because of the pressure in this location. The procedure used to fabricate the UV
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LED-based flexible substrate is illustrated in Figure 1a–c.
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Emission layer fabrication: Polymer powder (0.008 g) was blended into toluene (15 mL) and stirred for
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3 approximately 10 min. The polymer mixture was mixed with various ratios of the polymers (PFO:PFO-
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5 GreenB:PFO-DBT = 60:50:1 for 3800 K; PFO:PFO-GreenB:PFO-DBT = 100:100:1 for 5900 K),
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blended in PDMS at a ratio of 2:1, and then stirred for approximately 30 min. To produce the QD
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10 mixture, red, green, and blue CdSe/ZnS QD solutions (5 mg/mL) were prepared at different ratios
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12 (red:green:blue = 15:3:2 for 3700 K; red:green:blue = 15:10:1 for 5600 K), blended in the PDMS at a
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ratio of 2:1), and then stirred for approximately 30 min. The component ratio of each QD mixture was
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17 adjusted to have a similar correlated color temperature (CCT) to its PFO counterpart. Finally, we poured
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19 the polymer and QD mixtures into different glass molds and baked them at 40 °C for 8 h to produce
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22 polymer films and QD films. Because CCT determines how the human eye perceives a light source, we
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24 attempted to keep the CCT of each device similar when different emission layers were employed in the
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26 LEDs. The component ratio of each QD mixture was adjusted to have a similar CCT to its PFO
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29 counterpart. The procedures employed to combine the flexible emission layer and UV LED arrays are
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31 displayed in Figure 1d–h.
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RESULTS AND DISCUSSIONS
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36 Figure 2 presents the absorption and photoluminescence (PL) emission spectra of the PFO;
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38 GreenB; PFO-DBT; and red, green, and blue QDs. The PFO exhibited a strong emission band, peaking
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41 at approximately 420, 440, and 465 nm, and it emitted blue light, as shown in Figure 2a. Chartreuse and
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43 red rays were generated by the PFO-GreenB and PFO-DBT samples, respectively, which exhibited
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45 strong emission bands peaking at approximately 525 and 675 nm, as displayed in Figure 2b and c.
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48 Figure 2d–f presents the PL spectra of the blue, green, and red QDs, exhibiting strong emission peaks at
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50 approximately 450, 535, and 630 nm, respectively. The UV flip-chip was employed as a flexible
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52 shortwave pumping source because these materials had strong emission peaks in the UV region.
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55 When a current of 1.6 mA/cm2 was applied, the emission spectrum of one type of white flexible
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57 LEDs with QD and polymer mixture films yielded neutral white light, as indicated in Figure 3a and c,
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whereas the other type yielded warm white light, as shown in Figure 3e and g. As a function of injection
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current density ranging from 0.4 to 10 mA/cm2, the luminous efficiency and lumen flux of the neutral
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3 white and warm white flexible LEDs are presented in Figure 3b and d and Figure 3f and h, respectively.
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5 The inset photographs in Figure 3 show the neutral white and warm white PDMS layers fabricated from
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QDs or polymers. Both the polymer-fabricated neutral white and warm white flexible LEDs exhibited
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10 higher luminous efficiency than the QD-blended flexible samples (99.8% enhancement for the neutral
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12 white and 95.5% enhancement for the warm white light; obtained at a current of 3.8 mA/cm2). The
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luminous efficiency saturation as the current injection was increased was caused by a decrease in the
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17 efficiency of the UV chip. Figure S3 shows that the efficiency depends on the current density variation
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19 of a UV-based flexible LED. The 8.4% efficiency decrease at high current injection was a result of
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22 heating of the active region, carrier leakage, and Auger recombination.48-49 Carrier losses occurred either
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24 inside or outside the quantum well region due to nonradiative recombination. The phenomenon had little
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26 effect at low current but became dominant at high current injections.50 The quantum yield of the solid-
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29 and liquid-type QDs and polymer fabricated films of these photoluminescence materials is presented in
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31 Table S1. The major concern with a quantum-dot-embedded device is that the quantum efficiency drops
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when the solvent dries up because of self-aggregation.51-52 In addition to the self-aggregation effect,
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36 serious degradation of QD performance is observed when the device is exposed to air because of oxygen
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38 53-54
and moisture erosion. In our previous study, QDs in the liquid-type package for LEDs exhibited
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41 only a 5% decrease in performance after 1000 h of storage; however, once the solvent had dried up, the
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43 QDs tended to become the solid type and this led to a more than 70% reduction in performance.55 Thus,
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45 QDs in liquid form can be highly efficient, but they lose a large percentage of this efficiency when they
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48 solidify. Table S1 lists the measured quantum yields of the solid-type QDs used in this paper. We
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50 discovered that the polymer materials had superior quantum yields to the QDs; thus, it is conceivable
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52 that the efficiency of a polymer-based device is much higher than that of a QD-based device
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55 (Supporting Information, Figure S4).
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57 The polymer-fabricated flexible LEDs exhibited higher external quantum efficiency (EQE) than
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the QD-blended samples at both warm and neutral color temperatures (Supporting information, Figure
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S5). EQE was determined through an integrated sphere system in which all emitted photons were
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3 collected and their characteristics analyzed. The formula for calculating the EQE is as follows.56
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7 (1)
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where ∫λ/hcP(λ)dλ denotes total number of output photons and I/e indicates the number of electrons
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12 injected into the LED per second. In this study, the polymer films yielded higher brightness and
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14 quantum efficiency than did the QD films.
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17 Figure 4a–d presents the CRI and various Munsell codes (R1–R9) of the warm and neutral white
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19 flexible LEDs at a current density of 1.6 mA/cm2. The polymer-film-fabricated flexible LEDs achieved
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21 markedly higher CRIs (Ra) and CRI Nos. 1 to 9 (R1–R9) than the QD film samples. The polymer white
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24 flexible LEDs exhibited a high CRI of 90 and 96 at neutral and warm color temperatures, respectively.
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26 In addition to CRI, CRI R9 is a crucial criterion for lighting and is indicated by ability of strong red
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28 (scarlet) color rendering.57 The polymer-fabricated warm white flexible LED exhibited a high R9 (96) at
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31 3800 K, which we believe indicates that it can render the shape and hue of organic tissue. Although the
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33 color quality performance of the QD-film-fabricated LEDs was not as expected in this study, the QD-
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based devices are not necessarily poor. For example, QDs are good for display and yield a large color
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38 gamut.58-59 Regarding the CRI, studies have employed 675 QDs (CdS/ZnS:Cu) to optimize a white LED
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40 and improve its CRI Ra and R9.60-61 We believe that PL polymers and QDs are promising materials for
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43 use in flexible LEDs in the future. The CIE 1931 coordinates of the flexible LED devices in this study
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45 are plotted in Figure 4e. All of the flexible samples’ coordinates were within the proximity of the
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47 standard Planckian locus and were denoted as white light, which is suitable for many lighting
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50 applications.
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52 The CRI Ra and R9 variations of the QD-film- and polymer-film-blended flexible LEDs when the
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current was 0.04–10 mA/cm2 are illustrated in Figure 5. In this study, all CRI and R9 values obtained
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57 for the QD-blended white flexible samples were average, irrespective of whether they were driven by a
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59 low or high current. By contrast, the polymer-fabricated samples achieved very high CRI (96.6) and R9
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(99) when the current density was 5.2 mA/cm2. Moreover, the color quality of the polymer-blended
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3 samples not only yielded excellent rendering, but also remained stable when the current was varied.
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5 To verify the reliability of our flexible devices, we tested their performance under bending. Bending
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reliability was obtained when the QD-based and polymer-based flexible LEDs were subjected to
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10 different bending curvatures, as displayed in Figure 6a. In the bending test, the flexible samples were
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12 bonded onto the surfaces of cylinders with different diameters (D = 80, 60, 50, and 30 mm) (Supporting
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Information, Figure S6). According to the results, both of the flexible LED samples exhibited excellent
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17 bending reliability, as indicated by the luminous efficiency as a function of current, which varied
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19 nonsignificantly when the bending diameter was 30 mm. However, we found that once the bending
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22 diameter was smaller than 30 mm, the LED devices tended to pop up and detach from the flexible
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24 substrate. In addition to the bending test, the samples’ reliability was also tested through a thermal
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26 characteristic and lifetime test. The polymer-fabricated LEDs exhibited a lower surface temperature
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29 than the QD samples did, probably because the degraded conversion efficiency of QD devices generates
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31 more output heat 62-63 (Supporting Information, Fig. S7).
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CONCLUSIONS
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36 This study demonstrated flexible LEDs that generated warm white and neutral white light. White
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38 light was generated by the films blended with QDs and with polymer by using a UV flip-chip as the
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41 pumping source. The polymer film was blended with PFO, PFO-GreenB, PFO-DBT, and silicon glue
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43 and demonstrated higher luminous efficiency than the QD film samples did. Moreover, the polymer-
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45 fabricated warm white flexible sample exhibited a high CRI (Ra = 96 and CRI R9 = 96). In addition, the
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48 flexible LEDs were shown to be highly reliable when subjected to bending, thermal characteristic, and
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50 lifetime tests. We believe that these flexible white LEDs, which demonstrate excellent color quality and
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52 reliability, are suitable for use as surgery lighting and in special applications such as museum lighting
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55 ACKNOWLEDGMENTS:
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57 The authors express their gratitude to Epistar Corporation and Dexerials Corporation for their technical
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support. This research was funded by the Ministry of Science and Technology of Taiwan through grant
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numbers MOST 101-2221-E-009-046-MY3, MOST104-3113-E-009-002-CC2, and MOST102-2221-E-

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3 009-131-MY3.
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6 Supporting Information Available: The Supporting Information is available free of charge on the
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8 http://pubs.acs.org.
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12 For the experiments on the flexible substrate and details of the electrode layout design, the standard and
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14 datasheet has been marked; the reliability of the flexible devices, such as their quantum efficiency,
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16 depends on the current and storage lifetime characteristic; bending tests using different bending
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diameters and thermal distribution images have been investigated.
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