Materials Science and Engineering R 107 (2016) 142

Contents lists available at ScienceDirect

Materials Science and Engineering R

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

Recent advances in white organic light-emitting diodes

Zhongbin Wua , Dongge Maa,b,*
a
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, University of Chinese Academy of Sciences, Changchun
130022, Peoples Republic of China
b
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of
Technology, Guangzhou 510640, Peoples Republic of China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 22 March 2016 White organic light-emitting diodes (WOLEDs) are emerging as the most promising technology for the
Accepted 15 June 2016 next-generation display and solid-state lighting applications owing to their merits of being high-
Available online xxx efciency, low-cost, easy-exibility, and environment-friendly. In this review, we will discuss the
fundamental working principles, the basics of exciton manipulation concepts, the architecture designs
Keywords: within the emissive region, the approaches to relieve the efciency roll-off at high luminance, and the
White organic light-emitting diodes remaining challenges in all phosphorescent and hybrid WOLEDs. A comprehensive understanding of the
Exciton management exciton manipulation concept and the key factors dominating the WOLED performances is of great
Phosphorescent
importance for advancing technological applications. We aim to provide an overview on the recent
Hybrid
advances in WOLEDs with emphasis specically on: (a) principles on how to manipulate singlet and
Efciency roll-off
triplet excitons for maximizing the exciton utilization efciency; (b) exciton manipulation in all
phosphorescent WOLEDs and hybrid WOLEDs based on conventional uorophors or thermally activated
delayed uorescent emitters by nely designing the emitting layer architectures and selecting matched
materials; and (c) strategies to mitigate the efciency roll-off including the utilization of effective charge
and exciton-conned structures, decreasing the exciton lifetime, reducing molecular aggregation, and
broadening the exciton recombination zone.
2016 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Fundamental aspects of WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Basic working mechanism of WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. White emitting-light and device architectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Fluorescent and phosphorescent electroluminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.3. Frster and Dexter energy transfer processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.4. Direct exciton formation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.5. Light out-coupling enhancement techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Performance evaluation of WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.1. Device efciency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.2. CIE chromaticity coordinates, CRI and CCT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.3. Efciency roll-off at high brightness levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.4. Lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Basics of singlet and triplet exciton-manipulating concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Impacts of charge manipulation on device efciency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2. Singlet and triplet exciton diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

* Corresponding author at: State Key Laboratory of Polymer Physics and

Chemistry, Changchun Institute of Applied Chemistry, University of Chinese
Academy of Sciences, Changchun 130022, Peoples Republic of China.
E-mail address: mdg1014@ciac.ac.cn (D. Ma).

http://dx.doi.org/10.1016/j.mser.2016.06.001
0927-796X/ 2016 Elsevier B.V. All rights reserved.
2 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

3.3. Exciton-exciton annihilation and exciton-polaron quenching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4. All phosphorescent WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1. Single-EML phosphorescent WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2. Multi-EML phosphorescent WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3. Ultrathin non-doped phosphorescent WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.4. Tandem phosphorescent WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.5. Phosphorescent WOLEDs with singlet monomer/excimer dopant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.6. Remaining challenges and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. WOLEDs with conventional uorophors and phosphors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.1. Triplet harvesting strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.2. Single-EML hybrid WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.3. Multi-EML hybrid WOLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.3.1. Hybrid WOLED architectures with interlayer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.3.2. Hybrid WOLED architectures without interlayer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5.4. Remaining challenges and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6. WOLEDs with TADF emitters and phosphors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.1. Thermally activated delayed uorescence (TADF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.2. S-EML WOLEDs based on blue TADF materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.2.1. Single-molecule TADF systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.2.2. TADF exciplex systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
6.3. Multi-EML WOLEDs based on blue TADF materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.3.1. Complementary color architectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.3.2. Primary colors architectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
6.4. Remaining challenges and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7. Reducing efciency roll-off at high luminance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.1. Effective charge and exciton-conned structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2. Decreasing exciton lifetime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.3. Reducing molecular aggregation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
7.4. Broadening exciton recombination zone within EML . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
8. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

1. Introduction
Organic optoelectronic devices have been the most promising
candidates in todays emerging technology [1]. Since the milestone
study of organic light-emitting diodes (OLEDs) by Tang and
VanSlyke in 1987 [2], enormous efforts following the pioneering
work have been focused on the improvement of devices in terms of
their efciency, stability and color tunability, making them ideal
for the future display and ambient lighting [36]. Therein, white
OLEDs (WOLEDs) have drawn particular attention owing to their
favorable merits of high efciency, low cost, easy exibility, large
area, high resolution, and low energy consumption in the full-color
display and solid-state lighting applications [710].
White emission requires the mixture of either primary (red,
green, and blue) or complementary colors (e.g., orange and blue) to
cover the whole visible region as much as possible, i.e., from
380 nm to 780 nm. Due to the restricted spectral bandwidth of a
single emitter, multiple emitters are generally incorporated in one
device. Therefore, optimizing the matched materials-combination
and judicious device conguration are both necessary to obtain a
balanced and efcient white emission. After the rst work of
white-emitting devices was reported [11], much endeavor was
made to produce high-efciency WOLEDs. Although the initial
device therein exhibited the power efciency (PE) of < 1 lm W
1,
this value has already increased to nearly 100 lm W
1 during the
past few years [12], which surpasses that of uorescent lamps (70
90 lm W
1), offering a promising alternative.
To fabricate efcient WOLEDs, various approaches have been
proposed such as doping several uorescent/phosphorescent
emitters into the single-emissive layer (S-EML) [1320], or the
mutil-emissive layer (M-EML) [2133], combining the blue
exciplex host and the phosphorescent emitters [34,35], the
utilization of microcavity [36], the external heavy-atom effect
[37], the tandem structures [3840], the p-i-n junctions [41,42],
and the down-conversion architectures [43], the synthesis of
polymers [4447], introducing the multifunctional materials [48
54], using the triplet-harvesting strategy [55], the charge/exciton-
conned structures [56], and the light out-coupling enhancement
technology [5761]. Moreover, other physical effects that are
typical for organic emitting materials have also been introduced
for WOLEDs, e.g., combined the emission from blue and the formed
exciplex [6264], the united blue uorescence down-conversion
phosphorescence [65], and the mixture of exciplex and excimer
emission [66]. In fact, whatever advanced materials and subtle
device design architectures employed, the core is always related to
the manipulation of the singlet and triplet excitons in the device,
e.g., their generation, transportation, distribution and decay, etc.
This is because these physical processes will nally decide the
device performance for WOLEDs. According to spin statistics, the
recombination of holes and electrons is expected to generate
singlet and triplet excitons by 1:3 ratio under electrical excitation
[6770]. Thus, an essential requirement for achieving high-
efciency WOLEDs is that all the electrically generated singlet
and triplet excitons should be utilized for white emission. This
means the precise manipulation of singlet and triplet excitons is a
prerequisite key to realize the high-performance WOLEDs.
In this tutorial review, we will illustrate the exciton manipula-
tion concept to provide clues for developing high-performance
WOLEDs. This review is organized as follows. The introduction of
fundamental aspects of WOLEDs is presented in Section 2. After
that, Section 3 addresses the basic ideas of the exciton
manipulating concept and how this concept works in the operation
of WOLEDs. We then discuss the exciton manipulation application
in recently reported all phosphorescent WOLEDs in Section 4,
hybrid WOLEDs based on conventional uorophores in Section 5,
and hybrid WOLEDs based on thermally activated delayed
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 3

uorescent (TADF) emitters in Section 6, respectively. Thereafter, 2. Fundamental aspects of WOLEDs

we will discuss the strategies to reduce the efciency roll-off at
high luminance in Section 7. Finally, Section 8 gives a brief
summary of the challenges and prospects for the further
improvement of WOLEDs. Particular attention will be given to
the exciton manipulation concept application in WOLEDs and the
effective strategies to mitigate the efciency roll-off. The review
can help to explore the more effective method to design high-
performance WOLEDs.
2.1. Basic working mechanism of WOLEDs
2.1.1. White emitting-light and device architectures
As a source of white light, an ideal WOLED should emit a
continuous and wide spectrum, similar to that of natural sunlight
covering the full visible range as much as possible. In general, a
single emitter (both uorophores and phosphores) can only cover
some spectral fraction of the visible light, and cannot generate
white light if there is no additional exciplex or excimer emission
bands formed among the emitter molecules [66]. Thus, the white

Fig. 1. Various device congurations to produce white light in bottom-emitting WOLEDs using multiple emitters: (a) single-EML structure, (b) vertically stacked structure, (c)
multi-EML structure, (d) striped structure, e) blue OLEDs with down-conversion layers, and f) single-emitter based devices. For (a), (c), and (d): orange layers represent
organic functional layers, e.g. charge-transporting layers, not shown in (b) for better visibility. R, G, and B denote red, green, and blue, respectively. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of this article.)
4 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
light is produced by the mixture of complementary (e.g., blue and
yellow or orange) or primary colors (red, green and blue). The
matched materials-combination and device engineering are both
necessary to obtain a balanced and efcient white light. A
conventional bottom-emitting device comprises a transparent
electrode on top of a glass substrate, followed by one or more
organic layers and capped with a highly reective metal electrode.
Fig. 1 depicts the universal architectures of the WOLEDs using
multiple emitters.
As shown in Fig. 1a, S-EML structure has been considered as one
of the most convenient and simple approaches to white light by
incorporating multiple emitters (blue/orange, or red/green/blue)
into a single layer [1320]. Different luminophores give off their
own emissions, leading to a broad electroluminescence (EL)
spectra. Obviously, this structure can offer a very simple fabrication
process compared to the other approaches shown below. However,
the concentrations of the dopant emitters in WOELDs with the S-
EML need to be precisely regulated in order to realize the desired
EL spectra since a very small change in the dopant concentration
would lead to a pronounced variation in the energy transfer among
the emitting molecules. Moreover, with increased operational
voltages, the notorious spectra variations are always observed. To
obtain stable spectra, stacked WOLEDs (Fig. 1b), where each unit is
able to host an emitter, can be considered as an effective device
design concept [3840,71,72]. Whereas, the optical optimization
remains a big challenge since the emitters located far apart within
the cavity must be located at their respective eld antinode for the
efcient out-coupling [73]. Different from the above strategies, the
luminophores of different emitting colors can be placed in
individual layers to produce white light, called as the M-EML
(Fig. 1c), which can allow exible manipulation of each EML as well
as the precise control of exciton distributions or charges in
different EMLs [2133]. Accordingly, the content of different
colored light determines the quality of white light, so the general
challenge to design M-EML WOLEDs is to keep the emission from
different EMLs balanced, that is, a proper fraction of each color
should be emitted. Thus, it can be seen that the precise
management of charges and excitons is crucial for the desired
EL spectra. For example, to realize the balanced electron-hole
recombination, thin hole and electron blocking layers are usually
inserted between the EMLs to conne certain amounts of charges
in each of them. Meanwhile, to eliminate the additional interlayers
Fig. 2. Schematic illustrations of singlet and triplet energy levels of organic molecules under electrical excitation. For phosphorescent emitter materials, the created singlet
excitons can be efciently transferred to the triplet state via intersystem crossing (ISC); for TADF molecules, the formed triplet excitons can be efciently transferred to the
singlet state through a RISC.
among the EMLs for reducing the low driving voltage and
improving the efciency, much endeavor has been made to
manage the exciton distribution within the EML. Compared to the
S-EML, the multilayer concept provides a reliable strategy to
achieve superior efciency, stable color spectra and low efciency
roll-off simultaneously. Besides, as shown in Fig. 1d, the individual
device units emitting red, green and blue can be designed
separately through a strip approach instead of the stacked
structure to generate white light. The unique merits of these
striped WOLEDs include the tunability of the red, green and blue
light ratio in the resulting white light and convenience to address
sub-devices. However, the striped sub-devices should be fabricat-
ed rather small and close enough to eliminate the spatial color
inhomogeneity across the surface of WOLEDs in spite of the fact
that the diffuser foil can help relieve this issue [74]. Therefore, the
shadow mask with a sufcient resolution would be required to
form such emission patterns. Moreover, it involves complicated
constructing processes and higher current density for each color,
which accelerates the device degradation [75]. Even so, the
difculties associated with this type of WOLEDs still attract the
researchers interest. Apart from these concepts where high
technological efforts are necessary, other effective approaches
toward WOLEDs have been proposed, including the blue OLEDs
with external down-conversion layers (Fig. 1e) and the single-
dopants-based devices using the monomer/excimer emission
(Fig. 1f).
2.1.2. Fluorescent and phosphorescent electroluminescence
In organic semiconductors, charges are injected statistically
with respect to their electron spin, according to spin statistics, the
recombination of holes and electrons is expected to generate
singlet and triplet excitons by 1:3 ratio under electrical excitation
[6770]. Thus, the singlet fraction of 25% causes an OLED based on
conventional uorescent emitter molecules to be inefcient with
an upper limit of the internal quantum efciency hint = 25%,
because only the singlet excitons can be used for the emission,
whereas the triplet excitons generally undergo the non-radiative
process, as shown in Fig. 2.
As the appearance of phosphorescent emitter molecules, the
efciency of OLEDs was immensely improved [7678]. In general,
these phosphorescent materials are organometallic complexes
containing a noble heavy metal atom such as iridium (Ir), platinum
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
(Pt), palladium (Pd), osmium (Os), and so on [79]. Due to the heavy
atom effect, the spin-orbit coupling interaction is signicantly
enhanced, nally weakening the selection rule for previously
forbidden transitions in the triplet state of the molecules, which
leads to the strongly enhanced intersystem crossing (ISC) rates
between singlet state (S1) and triplet state (T1) [70]. Therefore, the
created singlet excitons can be efciently transferred into the
triplet states for radiative decay under electrical excitation. The ISC
rate is usually close to the unity in many phosphorescent systems.
Thus, the OLEDs based on the phosphorescent materials can
achieve a high efciency with the unity IQE (hint = 100%) [80].
Moreover, to reduce the bimolecular quenching processes includ-
ing the triplet exciton-triplet exciton annihilation (TTA) and the
triplet exciton-polaron quenching (TPQ) limiting the device
efciency at high luminance levels, the state-of-the-art phospho-
rescent emitters are especially optimized for very short excited
state lifetime-typically in the order of microseconds [81,82].
As known, because of the inherent disadvantages of rare metals
like the expensive cost, environmental pollution, unevenly
distributed resources, and being toxic, much research endeavor
has been made to explore alternative concepts to phosphorescence
that break the limit of hint = 25%. The concept of delayed
uorescence can make use of the high triplet exciton density via
the TTA process creating the delayed singlet excitons: T1 T1 !
S0 Sn [83]. The uorescent OLEDs based on the TTA has broken
the limit of hint = 25%, realizing the nearly 10% external quantum
efciency (EQE) [84], evidencing that it may be a valuable
alternative to phosphorescence. Considering the maximum hint =
62.5% in OLEDs via TTA, a recent breakthrough on the development
of TADF materials by Adachi and co-workers makes the more
efcient uorophores feasible [8590]. In the TADF processes, the
generated triplet excitons on emitter molecules can be harvested
by a reverse intersystem crossing (RISC) process induced by
sufciently small singlet-triplet energy gap (DEST), as shown in
Fig. 2, thus the TADF materials can achieve 100% exciton utilization
efciency, even comparable to the phosphorescent emitters [91
96]. Through a specially designed novel class of organic materials,
the DEST value could be reduced to approximate 80 meV, leading to
very high RISC rate [97]. Thus, a universal concept was proposed as
a promising alternative to the heavy metal complex based
phosphorescent emitters.
2.1.3. Frster and Dexter energy transfer processes
Excitons formed in a high band gap host are usually transferred
to any lower band-gap guest via either short range Dexter energy
transfer of triplet excitons or long range Frster resonance energy
transfer (the dipoledipole interaction) of singlet excitons [98].
However, WOLEDs are highly complicated because of the multiple
emitters-doped systems depending on the various energy transfer
mechanisms, which in turn lead to the exciton distribution on the
desired emitter molecules. Therefore, it is necessary for us to
briey review the Frster and Dexter energy transfers that can
happen between different molecular species.
Frster energy transfer is a non-radiative dipoledipole
coupling between donor (D) and acceptor (A) molecules. This
interaction may occur through occupied space, extending the
range of energy transfer and quenching [99]. The rate of Frster
energy transfer between the point dipoles can be written by [100]:


1 R0 6
kF 2:1
t Rd
where t is the exciton lifetime, Rd is the intermolecular distance
between donor and acceptor, and R0 is the Frster energy transfer
5
radius, expressed by:
Z
9hPL k2
R60 l4 FD lsA ldl 2:2
128p n5 4
Here, hPL is the photoluminescence (PL) efciency of donor, k is the
dipole orientation factor, n is the index of refraction of the medium
between donor and acceptor, l is the wavelength, FD is the area-
normalized donor emission spectrum, and sA is the absorption
cross-section of acceptor. As seen, this energy transfer depends on
both D and A transitions, which results in the following energy
transfer reactions:
D1 A1 ! D1 A1 2:3
D1 A3 ! D1 A3 2:4
We note that there is a triplet ground state conguration, giving
rise to A3 . As known, the energy transfer of the triplet states to the
singlet states is strongly forbidden in the Frster energy transfer
theory since it requires two simultaneous ISC steps. Whereas, this
will change if a phosphorescent donor is introduced. Due to the
strong spin-orbit coupling, the ISC process is enhanced, the
additional transfers are possible as following,
D3 A1 ! D1 A1 2:5
D3 A3 ! D1 A3 2:6
Although the transition from D3
to D1 requires the ISC process
and a lower rate than starting from D1 , these transitions may have
the same probability because the triplet exciton lifetime is usually
longer. The Frster energy transfer can overcome the distances of
up to 10 nm, which is much larger than the typical molecular
dimensions [101].
Compared to the Frster energy transfer, Dexter energy transfer
requires the orbital overlap of D and A, leading to a decreasing
interaction as the intermolecular distance increases. The resulting
energy transfer reactions are as follows:
D1 A1 ! D1 A1 2:7
D3 A1 ! D1 A3 2:8
Since the singlet state-singlet state interaction is an efcient
Frster-type transfer, it is rarely observed based on the exchange
interactions. In contrast, the triplet state-triplet state energy
transfer is very important since it offers the basis for efcient
triplet excited state transfer in OLEDs. The corresponding Dexter
energy transfer rate constant is [102]:
2p 2
2Rd =L
kD K Je 2:9
h
where K is a constant in units of energy [103]. The exponential
dependence on the intermolecular distance Rd evidences the
necessity of molecular orbital overlap. As seen, the Dexter energy
transfer is a short distance interaction, and the interaction distance
is typically below 3 nm.
2.1.4. Direct exciton formation processes
Except for the host-guest energy transfer, there is usually a
direct exciton formation process existing within the EML in various
WOLEDs. These two parallel pathways serve to channel the overall
excitons to both dopants, greatly reducing unfavorable energy
losses. In general, this color shift is closely related with the charge
trapping effect on guest molecules and the change of the exciton
6 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

recombination zone location with the increased operational

voltages [104]. We can make some assumptions to discuss the
relationship between the origin of the color-shift and the direct
exciton formation on emitter dopants. First, parts of holes injected
into the EML will be trapped by the emitters and then recombine
with the electrons that directly inject into the guest LUMO to form
excitons. Second, the electric eld mainly drops across the EML, in
consideration of the two large barriers at opposite sides of the EML.
Third, the electric eld is approximately constant within the EML.
Considering that both diffusion and drift mechanisms contrib-
ute to the hole charge trapping, the overall hole trapping rate t
1
Trap
can be dened as the sum of the diffusion- and the drift-induced
trapping rates expressed by:
D v
t
1
Trap tDiff tDrift

1
1
2:10
L2D LD

where t
1
Diff is the diffusion-induced trapping rate, tDrift is the drift-

1

induced trapping rate, D is the diffusion coefcient of holes, v is the

average drift velocity of holes. Since the electric eld is constant
within the EML, the hole mobility is also constant. The drift
velocity v can be described by the following equation:
mU
U0
v mjEj
d
where m corresponds to the hole mobility, U is the driving voltage,
U0 is the built-in potential, and d is the thickness of the EML. Thus,
the overall trapping rate t
1Trap can be expressed by:
D U
U0 m
t
1
Trap
L2D d LD
As stated above, the holes that are not trapped will traverse the
EML, the average time tTraverse it takes can be given by:
2
d d
tTraverse
v mU
U0
The inverse of this time t
1
Traverse corresponds to the traverse rate
at which the unperturbed holes transport through the EML. Here,
we dene RU as the ratio of hole-trapping rate t
1 Trap and hole-
traverse rate t
1
Traverse as follows,


2
t
1
Trap D d 1 d
RU 2:14
t
1 m LD U
U0 LD
Traverse
As seen, RU should be proportional to the ratio of the orange
(or, red and green) photon numbers and the blue photon numbers.
We can use the theoretical t to the experimental results,
evidencing whether the effect of eld-dependent competition
between hole trapping and undisturbed hole transfer is the actual
reason for the color-shift.
2.1.5. Light out-coupling enhancement techniques
In most conventional OLEDs, the glass with a refractive index of
1.5 is commonly used as transparent substrate, while the organic
materials used as the functional layers such as the charge-
transporting layers and exciton blocking layers typically have
refractive indices of 1.71.8. The difference in refractive indices
results in an optical interface between the organics and the
substrate, and the total reection can occur at the interface with a
rather portion of emitting-light being waveguided in the organic
layers. Except for the organic and substrate modes, the coupling of
the radiating dipoles to the plasmon states of the metal cathode is
another loss pathway. Thus, the resulting EQEs in OLEDs are always
limited to 25% assuming the light out-coupling efciency of 25%.
Fig. 3. Distribution of light modes and loss channels in a red phosphorescent OLED
as a function of electron-transporting layer (ETL) thickness that spaces the EML
from the metal cathode (from Ref. [105]). (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this article.)
2:11
Fig. 3 shows the different loss channels in a typical red
phosphorescent OLED based on a comprehensive optical model
[105]. By varying the thickness of the electron-transporting layer
(ETL), the rst and second eld antinodes were depicted. The
substrate modes follow almost the same modulation as the far-
2:12 eld modes showing distinct peaks. In contrast, the losses to
surface plasmon modes distinctly decrease, which is attributed to
the decreasing coupling interaction between emitting dipoles and
the surface plasmon mode. Meanwhile, the fraction of light being
waveguided in organic modes goes up with the increased ETL
2:13 thickness. Next, to obtain higher EQE beyond the upper limit, it is
indispensable to introduce the effective approaches to enhance the
light out-coupling efciency.
Many efforts have been undertaken to improve the light out-
coupling efciency of bottom-emitting OLEDs. The most straight-
forward way is to incorporate structured substrate surfaces such as
the pyramidal or lens arrays. The structured surface can decrease
the losses because the total internal reection is varied as the
normal to the surface changes. This light that cannot escape to air
because of total internal reection at the substrate/air interface can
easily be accessed by applying a macro-extractor to the substrate
surface, matching the refractive index of air. Other designs of
macro-extractors are truncated square-pyramid or owerpot-
shaped luminaires, it is noteworthy that their application is only
useful to quantify the amount of substrate-trapped light [119]. For
practical applications involving in the large-scale OLEDs, thin and
scalable concepts need to be applied to enhance the light out-
coupling. The utilization of the structured substrate surfaces or the
macro-extractors is often combined with other concepts applied
internally that aim to reduce the light inside the organic layers
(waveguide modes) [106]. To extract the light being waveguided,
introducing a square grid with a low refractive index material
between indium tin oxide (ITO) and the organic layers by means of
photolithography is an effective method [107]. Originally traveling
with a large angle to the OLEDs normal, these modes can be
converted to light having a smaller angle to the normal, entering
the escape cone of the device [119]. Compared to a reference
WOLED, the light output from a device with this out-coupling
structure increases by a factor of 1.32. Furthermore, applying a
microlens array leads to a 2.3-fold total improvement [107]. As
shown in Fig. 3, the losses to the surface plasmons are also severe,
Wu et al. made 120% enhancement for the integrated intensity by
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
increasing the distance between EML and metal electrode meeting
the second eld antinode of the system, which can be explained by
the increasing fraction of organic modes as the distance between
EML and metal electrode increases [61]. Besides, it can be noted
that the coupling of the emitting dipoles to the metal surface
plasmons signicantly contributes to the loss in OLEDs. The dipole
orientation of emitting dyes in host matrix was determined from
the analysis of the angle-dependent PL spectrum of the EML [108].
An emitter with a horizontal transition dipole moment usually
results in a much higher out-coupling efciency than the vertically
aligned dipole as demonstrated in polymers and organic small
molecules [109111]. Recently, not only uorescent molecules but
also some phosphorescent emitters have been reported to have the
preferred horizontal dipoles where a high EQE of beyond 30% is
expected [112,113]. In spite of the fact that the orientation of the
molecular dipoles depends on the precise molecule design, it
indeed provides an effective method to reduce the losses to surface
plasmon modes.
2.2. Performance evaluation of WOLEDs
2.2.1. Device efciency
Current efciency (CE, hCE ), power efciency (PE, hPE ), and
external quantum efciency (EQE, hEQE ) are the common
parameters used to evaluate the performance of WOLEDs. The
CE is the generally used to characterize the efciency of device
which can be evaluated by the naked eyes, which can be
calculated by:
L0o
hCE 2:15
J
where L0o is the luminance intensity measured in forward-viewing
direction, J is the current density through the device.
The gure-of-merit PE is the most relevant efciency value for a
WOLED in lighting applications, which is dened as the ratio of the
light output power weighted by the photonic sensitivity of the
human eye to the electrical power employed to drive the device.
Thus, it is written by:
f Dp
hPE hCE 2:16
U notorious color shift needs to be strictly controlled during the
where f D is a factor which depends on the light angular
distribution within the half-sphere in the forward direction,
p
Z2 Zp
1
fD Iu; fsinudfdu 2:17
pI 0
0
p
where I0 is the light intensity measured in the forward direction,
the emitting-light intensity Iu; f is a function of two angles
azimuthu and polar f.
The EQE is dened as the total number of photons emitted out
of the device by consuming per electron-hole pair injected into the
device. It can be calculated as follows:
f D pe
hEQE hCE 2:18
Kr Eph
where Eph is the average photon energy averaged over the whole
emission spectrum, the luminous efciency of radiation Kr is
calculated by:
Z 780
Fr lVldl
Kr 380Z 1 2:19
Fr ldl
0
7
where Fr l is the radiant ux andVl is the CIE 1931 spectral
luminous efciency of the human eye. An accurate EL spectrum
measurement is necessary for the correct derivation of the EQE
from the PE.
2.2.2. CIE chromaticity coordinates, CRI and CCT
Considering the application in solid-state lighting, WOLEDs
require not only a high device efciency, but also a high level of
color quality. Generally, Commission Internationale de LEclairage
(CIE) coordinates, color rendering index (CRI), and correlated color
temperature (CCT) are essential to evaluate the quality of white
emitting-light.
The CIE coordinates can be used to characterize the emitting
light color of a lighting source, which describes how the human
eyes perceive the emission color of any light source (with an
arbitrary emission spectrum) with a pair of two numbers (x, y) in
1931 CIE chromaticity diagram. The ideal white light point is
located at (0.33, 0.33) and the closer to the ideal white point, the
better the color purity.
WOLEDs as lighting sources should be broad and continuous
covering the entire visible-light spectral region so that the objects
with any color can be illuminated vividly by the produced white
light. CRI usually serves as a measure for this property, which
represents by a number between 0 and 100. A black body radiator,
by denition, has a CRI of 100. In WOLEDs, a CRI  80 is required for
indoor-lighting applications. In some areas such as lighting for
museum, studio, art gallery, medical application, and wide-color-
gamut display, the higher CRI (CRI  90) is crucial. More than three
colors are usually needed to achieve such high CRI [114,115].
CCT is another gure-of-merit factor to characterize the quality
of white light. It requires the CCT between 2500 and 6500 K for
high-quality white light sources. The ideal warm white point with
CCT of 2856 K, corresponding to the CIE coordinates of (0.448,
0.408), represents the chromaticity of tungsten incandescent
lamps, which has been widely considered as the most comfortable
articial light sources. In general, the warm white light needs the
CCT of below 5000 K, while the cool white light beyond 5000 K.
To obtain the high-performance WOLEDs, in addition to the
aforementioned parameters, the color stability should be also
taken into consideration in evaluating the lighting source. The
entire operational process, and the variation of CIE coordinates
should be small as much as possible.
2.2.3. Efciency roll-off at high brightness levels
Despite the signicant progress the WOLED technology has
made in terms of the efciency, CRI, color stability, and fabrication
cost during the past few decades, another issue remains unsolved:
the efciency of WOLEDs typically decreases at the high brightness
levels, an effect present in most WOLEDs known as efciency roll-
off. This can be caused by a range of different non-linear effects,
and it turns out that the underlying physics is complex [116]. The
efciency roll-off at high brightness levels can be quantied in
different OLEDs. Generally, the exciton quenching mechanisms
including triplet exciton-triplet exciton annihilation (TTA) and
triplet exciton-polaron quenching (TPQ) are responsible for the
efciency roll-off in phosphorescent OLEDs [117122].
In addition to TTA and TPQ, for uorescent OLEDs, the singlet
exciton-singlet exciton annihilation (SSA) [123,124] and the singlet
exciton-triplet exciton annihilation (STA) [125] may similarly play a
major role for the efciency roll-off at high luminance. Meanwhile,
the eld-induced quenching mechanism was also observed in OLEDs
[126]. The strength of eld-induced quenching relies on the exciton
generation process: bimolecular recombination under electrical
excitation leads to a larger average electron-hole distance than an
8 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
optical excitation, where charge-transfer states are formed. As a
consequence, the electrically formed charge pairs tend to suffer from
the eld-induced quenching than optically formed charge pairs
[127].
Besides the exciton quenching processes, the efciency of
exciton formation also depends on the current density, which may
represent a further potential origin of the efciency roll-off. At low
current densities, the charge imbalances are relatively common in
OLED structures since the energy barriers inside the layer stack are
different for electrons and holes. As a result, an initial increase in
external quantum efciency with current is often observed
[128,129]. At higher current densities, this charge imbalance
usually decreases since the injection barriers are easier to be
overcome [130]. Whereas, the charge balance may also deteriorate
with the increased voltages if the injection barriers are eld-
dependent, which further aggravate the efciency roll-off [131].
2.2.4. Lifetime
Lifetime is also an important parameter evaluating perfor-
mance of WOLEDs, and a long operational lifetime is essential for a
technology to achieve commercial success. However, the lifetime
of organic devices remains a major challenge that must be
overcome before the wide application of WOLED technology [132].
In addition to the intrinsic properties of the used materials, the
device structures also have a strong inuence on the device
lifetime. Many efforts have been made to improve the device
lifetime by regulating the EML structures. Forrest et al. demon-
strated a tenfold increase in blue PHOLED lifetime employing a
stacked PHOLED structure with two EMLs having graded phos-
phorescent dopant concentrations [133]. Grading used in combi-
nation with engineered frontier orbital energies of both dopant
and host materials signicantly decreases the exciton density
across the emission zone. This in turn increases the EQE of the blue
PHOLED while reducing detrimental TPQ that decreases device
lifetime. Qiu et al. presented a strategy to achieve WOLEDs with an
extremely long lifetime by wisely controlling the exciton
recombination zone. A mixed-host blue emissive layer was utilized
to broaden the exciton recombination zone. The lifetime of the
obtained WOLEDs Exhibits 40 times longer than that of the
conventional bilayer WOLEDs [134]. Adachi et al. demonstrated
highly efcient, stable OLEDs that emit via TADF by controlling the
position of the carrier recombination zone, resulting in projected
lifetimes comparable to Ir(ppy)3-based phosphorescent OLEDs
[135].
The well-known stretched exponential decay (SED) can be used
to t the luminance versus time curves obtained under different
driving conditions [136]. The SED is expressed as follows,
"
 #
L t b
exp
2:20
L0 t
where L0 is the initial luminance, t and b are the phenomenologi-
cal parameters. To predict the device lifetime LT50, where the
initial brightness decreases to the half of the peak, the calculating
process reads as follows,
LT50  Ln0 constant 2:21
Thus, according to the SED theory, we can calculate the device
lifetimes at different initial luminance.
3. Basics of singlet and triplet exciton-manipulating concept
3.1. Impacts of charge manipulation on device efciency
The EQE of OLEDs can be expressed as:
 
hEQE g  hg  FPL hout 3:1
where g is the charge balance of injected holes and electrons, hg is
efciency of radiative exciton production (hg 0.25 for uorescent
emitting materials, and unity for phosphorescent dyes), FPL is the
PL quantum yield of emitter molecules, and hout is the light out-
coupling efciency. When the emitting materials combination is
determined, hg , FPL , and hout will be generally decided. Thus, the
EQE value is closely associated with g. Assuming the recombina-
tion of free electrons and holes is Langevin-type recombination
process [137], in which the bimolecular recombination efciency
should be associated with g, which is a key factor. In an ideal
condition, the electrons and holes are injected and transported
equally well, and both charges can be conned within EML, and the
g value is close to the unity. However, in most WOLEDs, in which
multiple emitters are incorporated that sport exciton harvesting
abilities (e.g. triplet harvesting), the difference in electron and hole
charge mobilities within EML or between different functional
layers, and the energy barriers related to the mismatched energy
levels between the functional layers will make the ideal condition
very hard to achieve. Therefore, balancing the charge injection and
transporting property is essential to the realization of high
efciency. It has been shown that introducing bipolar hosts and
effective charge blocking layers are benecial to address this issue.
Compared to inorganic semiconductors, the intrinsic mobility of
organic materials is usually low, which can result in the higher
voltage required to achieve the correspondingly high brightness,
and thus signicantly decreasing PE. Hence, the operational
voltage must be reduced to achieve the higher PE by manipulating
the injected charges. One effective method is that by incorporating
charge transfer dopants into organic layers to increase the density
of charge carriers and hence the conductivity of organic layers, so
signicantly decreasing the driving voltage [7]. Other methods
including employing thin emissive layers [138], modifying electro-
des by introducing buffer layers [139,140], and designing a stepped
progression of the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) energy levels
between the functional layers that can facilitate charge injection
and transportation characteristics [141], are used to increase PE.
3.2. Singlet and triplet exciton diffusion
In WOLEDs, a balanced spectrum can be obtained by regulating
the energy transfer processes among EMLs. The singlet and triplet
exciton diffusion processes can inuence the device efciency and
the quality of white-emitting light. For instance, in uorescence/
phosphorescence hybrid WOLEDs, the triplet excitons formed on
uorescent molecules can be transferred to adjacent phosphores-
cent layers. There, they can be harvested, allowing close to exciton
utilization efciency of 100%. The diffusion of triplet excitons plays
a crucial role in the efciency and color stability. Meanwhile, the
exciton diffusion to quenching sites can reduce the efciency in
WOLEDs. It is therefore of great importance to manipulate the
exciton diffusion processes via regulating the device architectures,
especially for the EML structures.
The formed singlet and triplet excitons are strongly localized on
the emitting molecules, which are called as Frenkel excitons.
Nevertheless, they can still move by a series of incoherent jumps
between molecules via Frster or Dexter energy transfer process.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 9

Accordingly, the steady-state exciton density prole in the vertical The quintet states are usually higher in energy than the two initial
direction z of the stack is reduced exponentially with the increased triplet states and can thus be neglected. Possible pathways are as
distance from the interface of main exciton generation zone, based follows:
on the assumption of isotropic materials properties and lateral 
! T1 S0
homogeneity of all layers: T1 T1 ! X 3:4
! S1 S0
nX z n0 exp
z=LD 3:2
The total fraction of triplet excitons that can be converted into
singlet excitons by the multiple TTA processes is 15% [153]. For
p uorescent materials, TTA can generate more singlet excitons for
LD Dt 3:3 emission, thus increasing the efciency of the uorescent OLEDs
where LD is the exciton diffusion length, n0 is the exciton density at [154]. For phosphorescent systems, the generated singlet exciton
exciton generation interface, D is the diffusion coefcient, and t is during the TTA process can transfer back into the triplet excited
the effective exciton lifetime. state through an ISC process; even so, at least one triplet exciton
Since the radiative recombination from triplet state to singlet will be lost. Depending on the excited state lifetime, on the current
ground state is spin-forbidden, the triplet excitons typically take density, and hence on the triplet density, TTA may distinctly
about 106 times longer than the allowed singlet decay of 110 ns, decrease the efciency of phosphorescent OLEDs. The time
which leads to a triplet diffusion length that is often an order of evolution of triplet exciton population under electrical excitation
magnitude larger than that of singlet excitons (<10 nm). This can be written as,
provides an effective approach to spatially separate singlet and dnT t nT t 1 J


kTT nT t2 3:5
triplet excitons, which has been incorporated in the hybrid dt tT 2 qw
WOLEDs [142]. The uorescent emitters can be located close to
the exciton generation zone, whereas the phosphors are placed at a Here, the rst term describes the conventional and radiative
greater distance (between the singlet diffusion length and triplet monoexcitonic decay with the triplet lifetime tT , the second term
diffusion length), to some extent, the triplet excitons can diffuse accounts for the biexcitonic annihilation with TTA rate kTT , and the
through the interlayer, which ensures that the singlet and triplet third term represents the exciton generation. Then, the Eq. (3.5)
energies can be transferred to the uorophores and phosphors, can be solved to,
respectively, for being harvested for white emission. To fully nT0
nT t   3:6
exploit the triplet harvesting concept, however, the choice of
1 nT0 kTT2tT et=tT
nT0 kTT2tT
appropriate blue uorescent emitters and judicious device
engineering are necessary. Recently, a breakthrough on the where nT0 is the initial triplet exciton density without TTA.
development of thermally activated delayed uorescent (TADF) Assuming that the EL intensity (L) is linearly proportional to the
materials makes the more efcient blue uorophores with high T1 concentration of excited states, then the emission intensity is,
feasible [143]. Nowadays, the highly efcient blue TADF materials
with high T1 and PLQY have been successfully synthesized, and L0
Lt 3:7
used for WOLEDs, such as the combination of TADF-assisted 1 Ktet=tT
Kt
materials and conventional uorescent emitters [144], and the Under steady-state conditions, the EQE of an OLED can be
utilization of TADF blue exciplex systems in single-EML WOLEDs calculated by,
[145]. s !
It is therefore of considerable interest to investigate the hEQE J0 J
18
1 3:8
diffusion of triplet excitons in host materials and determine the hEQE0 4J J0
diffusion length. The general methods to determine the exciton
diffusion length are based on photocurrent measurements [146], with
and time- or spectral- resolved PL quenching [147,148]. Besides, the
4qw
methods using electrical rather than optical excitation were J0 3:9
kTT t2T
reported, which ensures that the excitons are formed in a conned
exciton generation region. The formed excitons can diffuse towards Using the values of kTT and tT obtained from the transient
a quenching material or a sensing layer. For a series of devices with measurements, the J0 values can be calculated. Accordingly, the
varying distances between generation and quenching region/ EQE of an OLED and the efciency roll-off with the increased
sensing layer, the different emission intensities are observed, and current density can be determined.
the experimentally obtained EL spectra of these devices can be TPQ occurs mainly by Frster transfer [119,127], and the
used to measure the exciton diffusion length [149,150]. differential equation can be written as,

3.3. Exciton-exciton annihilation and exciton-polaron quenching dnT t nT t J

kTP CJ1=l1 nT t 3:10
dt tT qw
The generated triplet exciton typically has a long lifetime, on Here, C is a constant which describes the electronic properties of
the order of 10
6-10
3 s [151]. As a result, large triplet exciton devices (e.g., the mobility, dielectric constant) and l is taken to
densities are produced at high brightness levels, leading to the unity according to the simple Mott-Gurney relation. The steady-
exciton density-driven quenching processes, such as the exciton state condition of Eq. (3.10) can be solved to,
exciton annihilation and exciton-polaron quenching. Therein, TTA
and TPQ are mainly responsible for the efciency roll-off in hEQE 1
3:11
common phosphorescent OLEDs. Likewise, in WOLEDs, they are hEQE0 1 tT kTP CJ1=l1
required to take into consideration for reduced efciency roll-off.
It can be noted that both TTA and TPQ mechanisms are usually
For TTA, the annihilation of two triplet states leads to an
taken into consideration, thus the exciton dynamical equation
intermediate state X, which can be transferred, according to spin
statistics, into one singlet, three triplet, or ve quintet states [152].
10 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

under operating conditions can be described by,

dnT t nT t 1 J 2J


kTT nT t2
kTP CJ1=l1 nT t 3:12 G 3:16
dt tT 2 qw qw

where e is the elementary charge, w is the width of exciton Eq. (3.13) can be used to t the obtained experimental EQEs of
formation zone, r is the polaron density, kTT and kTP are the rate phosphorescent OLEDs. Because both TTA and TPQ are closely
coefcients of TTA and TPQ, respectively. related to the triplet exciton density, we can decrease the density of
An steady-state solution (dnT t=dt 0) to Eq. (3.12) can be triplet excitons by regulating the EML structures, broadening the
used to describe the photon output per electron input, which is exciton recombination zone width, and decreasing the triplet
equivalent to the external quantum efciency hEQE. The solution is exciton density, thus mitigating the efciency roll-off.
as follows,
0v 1 4. All phosphorescent WOLEDs
u 2
hEQE uD G k D
B C
Q@t
TT

A 3:13 Phosphorescent materials can be commonly utilized to achieve
h0 kTT
2 kTT
high-efciency WOLEDs since they can harvest all electrically
generated singlet and triplet excitons through the efcient ISC
process. Various EML architectures have been investigated in all
qw phosphorescent WOLEDs. Therein, S-EML and M-EML structures
Q 3:14
tJ have been considered as the most effective approaches to superior
white light. Besides, high-performance all phosphorescent
WOLEDs can also be realized using a simple ultrathin nondoped


1 EML architecture. Moreover, tandem WOLEDs have attracted
D kTP CJ1=l1 3:15
t substantial attention, because they can simultaneously achieve a
high efciency and long lifetime. In this section, we will separately
present such advances on all phosphorescent WOLEDs according
to the different device architectures with different combinations of
phosphors and device structural engineering.

Fig. 4. Proposed energy level diagram of the designed S-EML WOLED and the chemical structures of host and guest materials.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 11

4.1. Single-EML phosphorescent WOLEDs
Due to the simple structure and low fabrication cost, much
attention has been paid to the S-EML structures in phosphorescent
WOLEDs. In spite of the these unique advantages, doping multiple
emitters in the S-EML would probably result in an energy transfer
from the short-wavelength emitters with high T1 to the long-
wavelength ones with lower T1, which would induce the notorious
color shift with the increased driving voltage or luminance.
Therefore, the concentrations of the phosphors in the S-EML
WOELDs need to be precisely controlled in order to realize the
stable white emission.
Forrest et al. reported a high efciency S-EML WOLED with
three phosphorescent emitters simultaneously doped in a host
[138]. The proposed energy level diagrams of the WOLED showing
the HOMOs and LUMOs relative to vacuum and the chemical
structures of used materials are depicted in Fig. 4. Owing to the
shallow LUMO level of 4,40 ,400 -tri(N-carbazolyl)triphenylamine
(TCTA) and the deep HOMO level of 1,3,5-tris(N-phenylbenzimi-
dazol-2-yl)benzene (TPBi), both the injected electrons and holes
can be effectively conned within the EML. And the energy gaps
(3.4 eV and 3.5 eV, respectively) of TCTA and TPBi are larger than
that of the blue emitter 40 ,60 -diuorophenylpyridinato)tetrakis(1-
pyrazolyl)borate (FIr6), which would prevent the exciton leakage

Fig. 5. (a) Energy diagram and device structure of the all-phosphor dual-color WOLEDs. The numbers in parentheses indicate the energy gaps of materials. T1: triplet energy.
EBL refers to electron blocking layer. (b) Proposed operational principle of the all-phosphor WOLEDs. Host-guest energy transfer dominates the blue emission, whereas the
orange emission is due to the direct charge-carrier trapping process. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)
12 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
and hence improve the exciton recombination probability. Besides,
the host material p-bis(triphenylsilyl)benzene (UGH2) with a very
wide energy gap also plays an important role in achieving the high-
efciency in the WOLEDs. The S-EML with the common host UGH2
can form a blue-green-red cascade energy transfer structure, the
triplet excitons on FIr6 molecules with high T1 can transfer to the
green fac-tris(2-phenylpyridine)iridium(III) (Ir(ppy)3) molecules,
and then transfer to the red phosphors iridium(III) bis-(2-
phenylquinoly-N,C20 )dipivaloylmethane (PQIr) molecules. As a
result, this structure can avoid the undesirable energy losses and
increase the device efciency. It can be seen that the resulting
WOLED exhibits the maximum EQE and PE of 12.0% and 26.4 lm
W
1, respectively. When the current density increases from 0.1 to
10 mA cm
2, the CIE coordinates remain relatively stable with
Dx = 0.05, Dy = 0.01.
To obtain high efciency and investigate deeply color-shift
mechanism in S-EML WOLEDs, Ma et al. reported a S-EML WOLED
with high efciency by incorporating two phosphorescent dyes,
namely, iridium(III)bis(4,6-(di uorophenyl)pyridinato-N,C20 )
picolinate (FIrpic) for blue emission and bis(2-(9,9-diethyl-9H-
uoren-2-yl)-1-phenyl-1H-benzoimidazole-N,C3)iridium(acetyla-
cetonate) ((fbi)2Ir(acac)) for orange emission in a single-energy
well-like emissive layer [155]. The systematic studies of dopants,
host and dopant-doped host lms in terms of photophysical
properties, transient PL measurements, current density-voltage
characteristics, and temperature-dependent EL spectra are subse-
quently performed, from which it can be concluded that the
emission natures of FIrpic and (fbi)2Ir(acac) are host-guest energy
transfer and direct exciton formation processes, respectively. These
two parallel pathways serve to the channels all generated excitons
to both emitter molecules for being utilized, greatly reducing
unfavorable energy losses. The proposed energy level diagram and
the operational principle of the WOLEDs are depicted in Fig. 5.
Furthermore, it is quantitatively proven that the competition
between the hole trapping on orange-dopant sites and the
Fig. 6. (a) Device conguration of the solution-processing WOLEDs. (b) EL spectra. (c) Power efciency-current efciency-luminance characteristics (from Ref. [163]).
undisturbed hole transporting across the emissive layer is the
actual origin of the color-shift. By precisely managing all the
electrically generated excitons, the resulting WOLEDs can achieve a
peak forward-viewing PE of 42.5 lm W
1, corresponding to an EQE
of 19.3% and a CE of 52.8 cd A
1.
For S-EML WOLEDs, solution-processed method becomes
highly attractive due to the unique merits of straightforward
simple fabrication procedure [156158] and the precise control of
the dopant concentrations of multiple emitters in EML [159,160]. In
this respect, one efcient way is using the mixed hosts consisting
of hole- and electron-transporting materials, which can improve
the charge balance and broaden the exciton recombination zone
within EML, to obtain high efciency WOLEDs [161,162]. Besides
the importance of balancing the charges, it is found that the control
of EML morphology and hole mobility is also crucial. As shown in
Fig. 6, a highly efcient solution-processed S-EML WOLEDs with
low efciency roll-off were demonstrated by the utilization of
mixed-host incorporating 1,1-bis[(di-4-tolylamino)phenyl]cyclo-
hexane (TAPC) with high-lying HOMO and high hole mobility into
TCTA [163]. It is clear that the injection and transport of holes and
the EML morphology are greatly improved due to the TAPC doping.
The resulting WOLEDs exhibited good device performances with a
maximum PE of 32.1 lm W
1. At the practical brightness of
1000 cd m
2, the PE still remains 23.3 lm W
1 with a driving
voltage of 4.6 V.
4.2. Multi-EML phosphorescent WOLEDs
Compared to the S-EML counterpart, the multi-EML structure
allows exible manipulation of each EML as well as precise
management of the charge and exciton distribution within EML. In
spite of the complication of device fabrication, the multi-EML
provides a reliable strategy for high-performance hybrid WOLEDs
with the achievement of superior efciency/CRI/color stability
trade-off.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
By using a common host for both blue and orange phosphores-
cent dopants separately doped into the dual-EML, a simple and
efcient WOLED was reported [164]. The common host can reduce
the unnecessary energy loss and be benecial for the energy
transfer from blue emitters to orange emitters, decreasing the
exciton loss. Through the analysis of device operational mecha-
nism, it is found that the blue dopant molecules (FIrpic) can
facilitate electron transport into the adjacent orange emitting-
layer. And the orange emission originates from both the direct
electron trapping by the orange dopant and incomplete blue-
orange energy transfer mechanisms. The resulting WOLED can
achieve a peak EQE of 16.9% and PE of 44.1 lm W
1. To realize 100%
exciton utilization efciency and further increase the efciency,
the generated singlet and triplet excitons needs to be more
precisely manipulated for utilization.
Indeed, by the careful manipulation of charges and excitons, a
universal approach to high-performance multi-EML WOLEDs with
the superior efciency/CRI/color stability trade-off was demon-
strated [165]. The key points include the utilization of a single-host
system and the wise arrangement of three-primary-color emitters.
Fig. 7a shows a multi-EML WOLED in which primary color emitters
are separately distributed with the R-G-B (where R is red, G is
green, and B is blue) sequence, and the device structures and EL
performances are shown in Fig. 7c. The resulting WOLED realized a
maximum forward-viewing PE and EQE of 41.3 lm W
1 and 20.1%,
respectively. The device color rendition is also impressive. The CRI
is calculated to reach as high as 85. Notably, this WOLED possesses
high color stability. When the luminance changes from 500 to 10
000 cd m
2, the variation of the CIE coordinates is rather small, CIE
x=0.38-0.9, CIE y=0.45-0.44. However, it can be noted that a small
color shift associated with the intense charge-trapping effect of the
Fig. 7. EL performances of mutil-EML WOLEDs. (a) Power efciency and EQE versus current density of the R-G-B WOLED. Inset: schematic structure of the device. (b) Power
efciency and EQE versus current density of a RG-B WOLED. (c) EL spectra of the R-G-B WOLED. (d) EL spectra of the RG-B WOLED (from Ref. [165]).
13
doped R species with the increased voltages is observed. To
eliminate the color shift, another multi-EML WOLED with RG-B
structure where R- and G- emitters are combined into one region
were proposed. Fig. 7b and d show the device structures and EL
performances of the RG-B WOLEDs. The resulting device efciency
remains the same high level, but the present EL spectra are rather
stable. In a wide range of operational voltages, the CIE coordinates
of (0.39, 0.42) are not variable, and the CRIs remain at 80. The color
shift is generally closely related with the change of the exciton
recombination zone and the charge trapping effect of dopant
emitters. Here, there is a certain charge trapping effect of the red
emitter molecules in R-G-B WOLEDs, while a very low red doping
concentration in the RG-B WOLEDs reduces this charge trapping
effect, and hence improves the color stability, evidencing that by
the precise manipulation of the charges and generated excitons
high-performance mutil-EML WOLEDs with superior efciency/
CRI/color stability can be realized. Similar to the most conventional
all-phosphor WOLEDs, the present device shows severe efciency
roll-off, the EQE of the RG-B device decreases to 13.6% at the
practical brightness of 1000 cd m
2, which should be further
improved in the future.
Recently, a subtle emissive zone structure was designed to
realize high-efciency multi-EML phosphorescent WOLEDs with a
reduced efciency roll-off [166]. By the precise manipulation of all
electrically generated singlet and triplet excitons, the resulting
WOLEDs show a maximum PE of 46.6 lm W
1, a CE of 46.4 cd A
1,
and an EQE of 22.4%. At the practical brightness of 1000 cd m
2,
these values remain as high as 41.3 lm W
1, 46.2 cd A
1, and 22.0%,
respectively, exhibiting less pronounced efciency roll-off. The
critical current density J0, where the EQE declines by half from its
peak, reaches as high as 220 mA cm
2. As known, the exciton
 14 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

quenching such as TTA and TPQ processes can result in the severe
efciency roll-off, both of which are strongly dependent on the
local exciton density. In this present WOLED, the quenching
processes are signicantly suppressed by the precise management
of charges and excitons. Fig. 8 shows the exciton recombination
processes in this WOLED. In this device, the common TCTA is used
as the host of red and green layers, which is also the same as the p-
doped and hole-transporting layers, thus it is very benecial to
transport the holes from the anode into the red and green emissive
layers without any barriers, reducing the unnecessary energy loss.
Moreover, the electrons injected from the cathode are also very
easy to transport into the blue EML due to the bipolar-transporting
property of 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine (26DCzPPy)
and the negligible barrier between 26DCzPPy and 1,3-bis(3,5-
dipyrid-3-yl-phenyl)benzene (BmPyPB), the bipolar-transporting
characteristic of 26DCzPPy also broads the exciton recombination
zone within the EML. To investigate the location and width of the
exciton recombination zone, ultrathin orange sensing layer
transferred at the different positions in the EML was inserted, as
shown in Fig. 9. Clearly, the main exciton recombination zone in
this device is located at the interface between the green region and
the blue region. Due to the high-lying triplet state FIrpic, the
formed excitons can transfer to the adjacent green emissive region,
and sequentially transfer to the red emissive region, leading to the
cascade-type energy transfer, decreasing the unnecessary energy Fig. 9. Relative orange emission intensities in OLEDs by inserting a 0.06 nm-
thickness orange sensing layer at different positions without green emitter doping
loss at the utmost extent. Additionally, due to the strong electron-
(a) and with green emitter doping (b). The applied voltage varies from 3.5 V to 5.1 V.
trapping effect of iridium(III)bis(2-methyldibenzo-[f,h]quinoxa- TCTA/26DCzPPy interface is set to be 0 nm. The inset gives the comparison of orange
line)(acetylacetonate (Ir(MDQ)2(acac)), the electron leakage from intensity from 0 nm to 5 nm in TCTA and TCTA: Ir(ppy)2(acac) layers (from Ref.
the red emission layer into the hole-transporting layer is [166]). (For interpretation of the references to colour in this gure legend, the
signicantly suppressed, thus conning the charge carriers within reader is referred to the web version of this article.)

the EML. It can be seen that the emissive zone structure balances
the charge carriers well, and effectively connes the excitons in a
broad exciton recombination zone. This greatly reduces the exciton
quenching in the EMLs, leading to the simultaneous achievement
of high efciency and reduced efciency roll-off in this mutil-EML
WOLED.
For lighting application, the simultaneously high efciency and
CRI are necessary. In this respect, the utilization of more than three
phosphorescent emitters has become a prerequisite [161,167]. Lu
et al. presented a four-color all-phosphor WOLEDs using the triplet
exciton conversion within the common organic layers in a cascade-
type emissive zone conguration [168]. Fig. 10 shows the device
conguration and the proposed energy diagram of the designed
devices. The resulting devices exhibited an EQE of 24.5% at
1000 cd m
2 with a CRI of 81, and an EQE of 20.4% at 5000 cd m
2
with a CRI of 85. As shown in Fig. 10b, the majority of excitons will
be formed near the CBP/TPBi interface before being harvested by
the dopant emitters. Since the blue emitter FIrpic has the closest
energy levels to both CBP and TPBI, the direct exciton formation on

Fig. 8. Proposed energy diagram and exciton recombination processes in the fabricated WOLEDs. The red, green and blue rectangles represent the corresponding color dopants,
respectively. represents the charge trapping effect, and is the energy transfer process (from Ref. [166]).
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 15

Fig. 10. (a) Device conguration and (b) proposed energy level diagrams of the designed four-color all-phosphor WOLEDs. The dopant emitters used are FIrpic for blue
emission (B), Ir(ppy)2(acac) for green emission (G), Ir(bt)2(acac) for yellow emission (Y), and Ir(MDQ)2(acac) for red emission (R). (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this article.)

the blue molecules is unlikely and it is critical to place the blue

emitter closest to the CBP/TPBi interface to harvest the excitons
rst to maintain enough blue emission. Moreover, the lower
energy-level green, yellow and red emitters are placed sequentially
next to blue EML to harvest excitons, forming a cascade-type
energy transfer structure. As mentioned above, this cascaded
structure design using a common ambipolar host CBP allows for
the exciton generation and recombination without introducing
other barrier layers that could induce undesirable charge
accumulation and energy loss, reducing the notorious triplet-
polaron quenching. It is also noted that there is no interlayer
inserted between two adjacent emitting layers in this WOLEDs, so
that the surplus excitons can readily diffuse into the adjacent layer
having a lower energy level for being harvested.
4.3. Ultrathin non-doped phosphorescent WOLEDs
Doping free OLEDs have attracted substantial researches
because the fabrication processing is very easy in a simple way
[169,170]. By introducing an ultrathin undoped orange emitting
layer (less than 1 nm) adjacent to the electron-transporting layer,
high efciency orange and four-color white OLEDs have been
demonstrated [161]. The ultrathin un-doped orange OLEDs showed
a high EQE of 16.4% at 1000 cd m
2, and the resulting four-color
white OLEDs emitted an EQE of 15.5% and a CRI of 87 at the
luminance of 1000 cd m
2. As shown in Fig. 11, the resulting four-
color WOLEDs exhibit very superior white emitting light, and the
CRI reaches as high as 89 at a brightness of 100 cd m
2. For the case
of above WOLEDs, its EQE can be simply expressed by,
hwhite xB hB xG hG xO hO xR hR 4:1
16 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 11. (a) EQE-current density characteristics of the four-color WOLED and four
monochrome OLEDs. (b) EL spectra of the white OLED at different luminance levels.
(c) EL spectra of the four color white OLED at 1 mA cm
2, the tting white emission
spectrum and the four monochrome OLEDs EL spectra (from Ref. [161]).
where hwhite , hB , hG , hO , and hR are the EQE of white, blue, green,
orange, and red OLEDs, respectively, and xB , xG , xO , and xR are the
fractions of excitons harvested by blue, green, orange, and red
dopants. From Fig. 11a, hB , hG , hO , hR xB , xG , xO , and xR are 17.6%,
18.2%, 16.8%, 10.8%, 11.1%, 15.8%, 28.4%, and 44.7%, respectively.
According to Eq. (4.1), the hwhite value can be calculated to be 14.4%.
It can be seen that this value agrees well with the measured value
of 15.5%, indicating the validity of the introduced ultrathin
undoped orange emitting layer in exciton utilization. It can be
seen that the main reason for the low hwhite is due to the lower
value (10.8%) of hR . Therefore, by using a much more efcient red
emitter, the EQE of above WOLEDs should be able to be further
improved.
For ultrathin un-doped type WOLEDs, obviously the thickness
and position of ultrathin un-doped emissive layer are very
important in the effective utilization of the formed excitons, thus
realizing high efciency. Recently, a high-efciency WOLED with
an ultrathin un-doped orange EML sandwiched between two blue
EMLs was reported [171]. In order to obtain high efciency, a bi-
layer blue EML with hole-transporting TCAT host and bipolar
transporting 26DCzPPy host, respectively, were designed, and the
thickness of ultrathin un-doped orange EML has been optimized. It
can be seen that the optimized WOLEDs show the maximum PE,
CE, and EQE reach 63.2 lm W
1, 59.3 cd A
1, and 23.1%, respectively,
which slightly decrease to 53.4 lm W
1, 57.1 cd A
1, and 22.2% at
1000 cd m
2, showing low efciency roll-off. And it also exhibits
balanced EL spectra with the CIE coordinates of (0.41, 0.44) at a
practical brightness of 1000 cd m
2. Fig. 12 shows the WOLED
structure, chemical structures of the materials used, and the
proposed energy-level diagram. Due to the obvious impact of the
ultrathin Ir(bt)2(acac) layer on the device performance, through
the regulation of the ultrathin orange emissive layer thickness, the
management of created excitons can be realized.
Fig. 13 shows the EL performance of the fabricated WOLEDs
depending on the thickness. As seen, when varying the thickness of
orange layer, the change of current density-voltage characteristics
is negligible. However, the device performance shows the
thickness dependence. A further investigation of the exciton
recombination zone was made. Thus, the ultrathin layer can be
used to determine the location and width of the exciton
recombination zone within the EML. By transferring the ultrathin
sensing layer through the overall EML, the different intensities of
the orange emission dependence on the location of the sensing
layer can be obtained, indicating that in this EML conguration the
exciton recombination zone locates near the TCTA: FIrpic/
26DCzPPy: FIrpic interface.
Furthermore, on the basis of the ultrathin un-doped concept,
the complementary blue/orange, three primary red/green/blue,
and four color red/green/orange/blue WOLEDs with ultrathin EMLs
can be fabricated [172]. As shown in Fig. 14, the inserted interlayer
between ultrathin un-doped EMLs can effectively prevent the
exciton quenching among EMLs, which can improve the device
efciency. By this judicious management of the excitons, the
resulting BO, RGB, and ROGB WOLEDs exhibited the maximum
EQEs of 16.4%, 18.5%, and 10.8%, respectively. It is of importance to
optimize the transporting layers at both sides of the EML to achieve
more effective exciton connement, and reduce the exciton
quenching, this further improving the device performances. All
three types of WOLEDs should be very easy to fabricate and the
color of each device can be easily tuned by changing the thickness
of the TCTA interlayer. The design concept of the ultrathin un-
doped EMLs in a simple way provides valuable avenues in the
future practical application as a result of wise material choice.
4.4. Tandem phosphorescent WOLEDs
Instead of separating the different emitters required for the
white emission into the distinct EMLs, WOLEDs can also be realized
by connecting a set of complete unity OLED emitting with the
different regions of emissive via charge generation layer (CGL)
[173], called tandem WOLEDs, as shown in Fig. 15. The motivation
for using the tandem concept is to increase the efciency and
stability of OLEDs. Instead of obtaining at most one photon per
injected charge, tandem OLEDs can generate multiple photons per
unit charge. However, this comes at the cost of increased operating
voltage. The power efciency of such tandem OLEDs cannot,
therefore, be higher than for that of the unity OLEDs [174,175].
Fortunately, by optimizing the CGLs, thus precisely manipulating
the generated charges and excitons, the PE of the resulting tandem
WOLEDs can also be greatly improved, which has been proved by
many literatures [176,177].
Recently, Kido et al. reported the fabrication of a multi-OLED
comprising two light-emitting units (LEU) and a CGL between the
ITO anode and Al cathode using only solution-based processes
[182]. Combining the polyethyleneimine-ethoxylated (PEIE)/ZnO
as the electron injection layer, the driving voltage and efciency of
the fabricated multi-OLED are the sums of corresponding values of
the component LEUs. These results demonstrate that the solution-
processed CGL successfully generated electrons and holes, and that
the generated electrons and holes were injected into the 1st-LEU
and the 2nd-LEU, respectively, when a voltage was applied,
resulting in charge recombinations in each LEU.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 12. Device structure of the ultrathin un-doped structure WOLEDs. (b) Chemical structures of the materials used in this study. (c) Proposed energy diagram of the device
(from Ref. [171]).
Actually, compared to the conventional WOLEDs, tandem ones
offer several advantages. First, tandem WOLEDs seem to be less
susceptible to voltage-dependent color shift. In a tandem OLED, the
current density in each unity will be same. As a result, the
brightness ratio between the individual sub-stacks will not change
with the increased operational voltages, indicating that the stable
EL spectra. Second, as we know, the lifetime of OLEDs depends on
the current density in the device in a strongly super-linear manner.
If the current density can be reduced by two or three times, the
device lifetime will increase by a factor of four or nine. The stacking
concept allows such a reduction of the applied current without
decreasing the overall brightness, which might be one of the most
important advantages in tandem WOLEDs [178]. Third, a rene-
ment of the tandem concept is that the devices allow the individual
unity devices within the stack to be spatially separately addressed
[179]. The emission color of such devices can be easily tuned by
regulating the current density in each sub-device. By judiciously
and precisely manipulating the generated excitons, the tandem
WOLEDs can achieve simultaneously the improvement of PE,
reduced efciency roll-off and superior color stability.
Nowadays, one of the main challenges in developing high-
performance tandem WOLEDs is to nd suitable materials for
CGLs. Early tandem OLEDs used vanadium pentoxide (V2O5) as the
interconnectors [38]. Later, MoO3 offers good optical transparency
and its high work function of 5.3 eV [180], compared to V2O5,
forming an efcient hole-injecting contact with the sub-cell in
which it forms the anode, which has been accepted as a promising
CGL [39]. Recently, organic semiconductor heterojunctions such as
HAT-CN/HAT-CN:TAPC/TAPC served as efcient CGLs have
17
achieved rather high EQE and CE in tandem OLEDs, and PE is
also greatly improved due to the efcient charge generation effects
of organic semiconductor heterojunctions [21,181,182], which will
be very important for the realization of high power efciency
WOLEDs.
4.5. Phosphorescent WOLEDs with singlet monomer/excimer dopant
However, the utilization of multiple layers or dopants can lead
to some possible operational challenges like the voltage-depen-
dent emission and color-aging effects due to differing electrical
properties or degradation processes for each emissive dopant or
emissive layer [62]. One solution to address these issues and for
simplifying the device structure is the development of singly-
doped white OLEDs by utilizing the monomer/excimer properties
of square-planar Pt complexes. For example, The rst demon-
strations of excimer-based white devices employed platinum
complexes containing uorinated cyclo-metalating ligands such as
platinum(II) [2-(40 60 -diuorophenyl)pyridinato-N,C20 ]2,4-penta-
nedionato (FPt) [63], which exhibited maximum EQE of 15.9%
and low CRIs. Recently, Li et al. reported WOLEDs utilizing
platinum (II) bis(methyl-imidazolyl)benzene chloride (Pt-16),
demonstrated the achievement of CIE coordinates of (0.33,
0.33), a CRI of 80, and an improved maximum EQE of 20.1%
[64]. Further, they demonstrated a symmetric tetradentate cyclo-
metalated platinum complex, Pt707, showing extremely high
efciency in both monomer and excimer emission [62]. The
resulting blue device employing Pt7O7 as emitters realized a peak
EQE of 26.3% and CIE coordinates of (0.12, 0.24), which is even
18 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 13. EL performance of the resulting WOLEDs. (a) Current density-voltage-luminance characteristics of devices with varied thicknesses of Ir(bt)2(acac). (b) Current
efciency, (c) power efciency, and (d) external quantum efciency as a function of luminance at different thicknesses of 0.02 nm, 0.04 nm, 0.06 nm, and 0.08 nm (from Ref.
[171]).

Fig. 14. Device structures of the WOLEDs based on ultrathin un-doped EMLs. R, G, O, and B represent red, green, orange, and blue, respectively (from Ref. [172]). (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

comparable to that of the state-of-the-art blue phosphorescent 100 h at elevated current densities of 20 mA cm
2. Thus, this
OLEDs. And the white device exhibited a peak EQE of 25.7% and CIE approach offers a very simple route to realize broadband, white
coordinates of (0.37, 0.43). Moreover, both devices displayed emission from one single molecule by adjusting its doping
impressive device operational lifetimes values, LT50, of 36 h to over
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 19

Fig. 15. Schematic diagrams of the tandem WOLEDs. (a) A tandem WOLED (tandem A) based on TPBi: Li2CO3/TCTA: MoO3 as the charge generation layer (CGL). (b) A tandem
WOLED (tandem B) based on interface-modied C60/pentacene organic heterojunction as the CGL (from Ref. [173]).

Fig. 16. HOMO and LUMO levels (solid lines) of materials used in the triplet harvesting hybrid WOLEDs, and exciton (S0, S1, and T1) energy diagram of the emitter layers. The
exciton generation from free charge carriers takes place close to the 4P-NPD/TPBi: Ir(ppy)3 interface. There, the energy transfer processes (Frster and Dexter energy transfer)
are possible (solid arrows), which determine the ratio of blue uorescence to green phosphorescence but do not reduce the quantum efciency. Triplet excitons in 4P-NPD can
also diffuse towards a-NPD layer (dashed arrow) where they can still be harvested by orange phosphorescence (from Ref. [41]). (For interpretation of the references to colour
in this gure legend, the reader is referred to the web version of this article.)
20 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
concentration in an appropriate host, great simplifying the device
structure.
4.6. Remaining challenges and prospects
In the past decades, all phosphorescent WOLEDs have drawn
substantial interests in both scientic and industrial elds. Their
favorable merits such as high efciency and low driving voltage
would make them the most competitive candidates for the next
generation full-color display and lighting sources.
However, in order to better meet the requirement of practical
application, all phosphorescent WOLEDs still confront several
challenges to be urgently addressed. First, the white emission in
many devices is often relatively far away from the Planckian locus,
which would lead to the undesirable hues of emitting light. This
may be attributed to the imprecise doping concentration of the
dopant emitters. To obtain the balanced and desirable WOLEDs, the
emitter concentration doped into host materials must be precisely
controlled, which can be realized by the precise management of all
electrically generated singlet and triplet excitons with judicious
regulation of the device congurations.
Due to the absence of efcient and stable blue phosphorescent
emitters, all phosphorescent WOLEDs have always been blamed
for their short device lifetimes. Thus, the development of stable
deep-blue emitting phosphors and judicious device designs will be
of great importance to produce high-performance all phosphores-
cent WOLEDs to match the commonly accepted white-points,
while maintaining good CRI at the same time.
In 2009, Leo and co-workers presented an OLED structure that
combines a novel concept for energy-efcient photon generation
Fig. 17. Proposed diagrams of singlet and triplet excitons decay on host molecules under different doping concentrations within the EML (from Ref. [184]).
with improved out-coupling [12]. By utilization of the light out-
coupling techniques including an index-matched glass half-
sphere, patterned surface, and locating the EML away from the
reective cathode to reduce the plasmonic losses, they have
achieved PE of 90 lm W
1 (34% EQE) at the practical brightness of
1000 cd m
2, higher than the average PE of uorescent tubes.
However, the most WOLEDs still suffer from the severe efciency
roll-off at higher luminance, which is a crucial factor requiring to
be addressed. By further optimizing the structures, broadening the
exciton recombination zone, and precisely manipulating the
exciton distribution, high-performance WOLEDs can be realized
and the further investigation of the WOLEDs are being on. We look
forward to these exciting developments in all phosphorescent
WOLEDs in the forthcoming years.
5. WOLEDs with conventional uorophors and phosphors
Recently, hybrid WOLEDs have drawn considerable attention
due to their unique advantages of combining the excellent stability
of blue uorophores and the high efciency of long wavelength
phosphors [55]. In general, hybrid WOLEDs can be constructed
using two EML architectures, including multi-EML or S-EML with
different color emitting dopants. The concentrations of phosphors
in S-EML hybrid WOELDs need to be precisely controlled. As an
alternative, the multi-EML counterpart can achieve better EL
performance despite its complexity of device fabrication. In this
section, we will illustrate the recent advances of S-EML and multi-
EML hybrid WOLEDs, from which we can experience the rapid
developments of hybrid WOLEDs.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 21

Fig. 18. (a) Device structure and proposed operational mechanism diagram in the hybrid WOLEDs with single-EML. (b) EL spectra of the device. (c) Power efciency-external
quantum efciency-luminance characteristics. Inset: current density-luminance-voltage characteristics (from Ref. [185]).
22 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
5.1. Triplet harvesting strategy
Most blue uorescent dyes used as dopants for highly efcient
blue OLEDs exhibit low triplet states. The commonly used blue
dopant DSA-ph, for example, has a low triplet state of 2.0 eV, which
is even lower than that of red phosphors [183]. The reverse energy
transfer from the phosphorescent emitter to the low-lying triplet
state blue uorescent emitter signicantly quenches the excitons,
indicating that the device cannot intrinsically reach the exciton
utilization efciency of 100%.
To reduce the exciton losses, Leo et al. proposed the triplet
harvesting concept [41]. They used a blue uorophor with a small
singlet-triplet splitting energy as a bulk emission layer wherein the
singlet and triplet excitons are intentionally generated. Fig. 16
shows the energy transfer diagram of the hybrid WOLEDs based on
the proposed triplet harvesting concept. The triplet state of the
used blue uorophor N,N0 -di-1-naphthalenyl-N,N0 -diphenyl-
[1,10 :40 ,100 :400 ,1000 -qua-terphenyl]-4,4000 -diamine (4P-NPD) lies higher
than the triplet state of at least one of the used phosphors, there is
not only no phosphorescence quenching anymore, but also can the
intrinsically non-radiative triplets on the blue uorophor now be
harvested for the emission by being transferred to adjacent
phosphor emitter molecules. The generated singlet excitons are
used for blue uorescence directly within this layer which ensures
they do not lose energy from their generation until their radiation.
It can be seen that the device can achieve the PE of 22.0 lm W
1,
corresponding to 10.4% EQE. By applying a micro-lens out-coupling
foil, the light emission in forward direction is continuously
enhanced, leading to 28.0 lm W
1 (12.9%) at 1000 cd m
2. The
measurement of the total external efciency within an integrating
sphere then gives 57.6 lm W
1 (20.3%) at the brightness of
100 cd m
2 and 37.5 lm W
1 (16.1%) at 1000 cd m
2, indicating
the effectiveness of the triplet harvesting concept.
5.2. Single-EML hybrid WOLEDs
Single-EML structures have become one of the ways that
fabricate hybrid WOLEDs due to the advantage of simple
processing, such as solution methods, which is considered to be
an important technology for future low-cost and large-area
manufacturing. As we now, single-EML is very susceptive to the
doping concentration of emitters, a small variation in the dopant
concentration would result in a pronounced change in the energy
transfer between the emitting dopants, resulting in the color-shift.
Thus, when constructing the high-efciency S-EML hybrid
Fig. 19. Exciton energy diagram for a blue uorophor and a phosphor: (a) the triplet state of uorophor lower than that of phosphor and (b) the triplet state of uorophor
higher than that of phosphor. Modied from Ref. [55]. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this
article.)
WOLEDs, it is essential to precisely control the doping concentra-
tion.
A simple method to fabricate S-EML hybrid WOLEDs is doping a
red phosphor into a blue uorophor host by an efcient doping
concentration regulation strategy, which effectively separates and
respectively utilizes the singlet and triplet excitons. For example, a
high efciency S-EML hybrid WOLED has successfully fabricated by
doping 0.1 wt% tris(2-phenylquino-line)iridium(III) (Ir(2-phq)3) in
2,8-di[4-(diphenylamino)phenyl]dibenzothiophene-S,S-dioxide
(DADBT) [184]. The resulting WOLED shows good EL performances
with a low turn-on voltage of 2.4 V, maximum total EQE, CE and PE
of 26.6%, 53.5 cd A
1, and 67.2 lm W
1 (the total efciency  1.7*
forward-viewing efciency), respectively, indicating the effective-
ness of S-EML structure to fabricate high-efciency hybrid
WOLEDs. Due to the bipolar-transporting property of DADBT,
the formed excitons would be mainly located on the blue
uorescent molecules. For this case, there are three kinds of
emission processes depending on the doping concentrations, as
shown in Fig. 17. For this case of a very low orange phosphorescent
concentration, some of the host uorophor molecules would nd
no phosphorescent dopant molecule within its vicinity of triplet
diffusion length (RT). The triplet excitons on the blue uorescent
molecules cannot be transferred to the phosphorescent dopant
molecules (Fig. 17d). Therefore, the singlet excitons on these
uorescent molecules can radiatively decay to emit blue light, and
the triplet excitons would decay nonradiatively. When the doping
concentration is increased, some uorescent molecules would nd
the phosphorescent dopant molecules within their vicinity of
singlet diffusion length (RS), the phosphorescent molecules do
exist within RT. The singlet excitons on such uorophors can be
used for the blue emission, and the triplet excitons can transfer
their energy to the dopants for phosphorescent emission (Fig. 17e).
With the further increase of the doping concentration, in this case,
the uorophors with phosphorescent dopants are within RS
distances, all the excitons generated on these uorophors would
transfer their energy to the dopant molecules for phosphorescent
emission. It can be seen that by regulating the doping concen-
trations within a reasonable range, as shown in Fig. 17b, the
generated singlet excitons on the blue uorophors can be used for
the blue emission, and other excitons will transfer for the
phosphorescent emission, achieving 100% IQE.
As known, the complementary-color WOLEDs generally exhibit
very low CRI. To improve the CRI, a simplied way is co-doping
green and red phosphors into the same blue uorophor host. Fig. 18
shows the device structure, proposed working mechanism, and EL
performances of the reported WOLEDs by co-doping red and green
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 23

Fig. 20. (a) External quantum efciency-power efciency-current density characteristics of the multi-EML hybrid WOLEDs. Inset denotes the device conguration. (b) EL
spectra of the WOLEDs at different current densities. (c) Proposed energy transfer mechanisms (from Ref. [142]).
24 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

phosphors into blue uorophor bis(2-[2-hydroxyphenyl]pyridi-

nato) beryllium (Bepp2) as the emissive layer. Here, Bepp2
simultaneously acts as the blue emitter, electron-transporting
material, and high triplet energy host for the phosphors and the
concentration of red and green phosphors is controlled at 0.3 wt%
[185]. It can be seen that this simple device emits good white light
with three separated red, green and blue peaks, which are
obviously from red phosphor, green phosphor and blue uorophor,
respectively, resulting in CRI of 88, and exhibits the maximum
forward-viewing PE and EQE of 46.8 lm W
1 and 16.5%, respec-
tively. Moreover, the maximum CRI reaches up to 90. Since Bepp2
has higher singlet and triplet energy levels than that of Ir
(ppy)2(acac) and Ir(PPQ)2(acac), the sequential energy-transfer
steps can be assumed, either initial Bepp2 to Ir(ppy)2(acac) and Ir
(PPQ)2(acac) by singlet energy transfer followed by an efcient ISC
process to the triplet energy of Ir(ppy)2(acac) and Ir(PPQ)2(acac), or
direct triplet energy transfer (Dexter transfer) from Bepp2 to (Ir
(ppy)2(acac) and Ir(PPQ)2(acac), resulting in the red and green
emission of phosphors. Because the Dexter transfer, which is
typically short-range energy transfer, can be eliminated due to the
very low concentration of Ir(ppy)2(acac) and Ir(PPQ)2(acac) within
EML, leading to the lumorphores located beyond the effective
Dexter-transfer radius of the excited molecules. Although the S-
EML WOLEDs can also realize high efciency and CRI values, the
spectral variation with luminance is inevitable, which is also the
intrinsic property of S-EML WOLEDs with complicated operational
mechanism.

5.3. Multi-EML hybrid WOLEDs

Compared to S-EML hybrid WOLEDs, multi-EML counterparts

offer a exible manipulation of each EML as well as precise
regulation of the charge and exciton distribution in distinct EMLs.
In spite of the complexity of the device fabrication, better EL
performance can be achieved. Thus, the multi-EML structures
provide a reliable strategy to fabricate hybrid WOLEDs. In this
section, we will separately discuss the multi-EML hybrid WOLEDs.
The survey of the reported multi-EML hybrid WOLEDs shows
that blue uorophors play an important role in the management of
singlet and triplet exciton distribution. There are commonly two
different situations when comparing the triplet states of uo-
rophor and phosphor: (i) the rst triplet state of uorophor (T1,f) is
lower than that of phosphor (T1,p), (ii) T1,f is higher than T1,p, as
shown in Fig. 19 [55]. In the case of T1,f < T1,p, the triplet energy can
transfer from phosphor to uorophor, resulting in non-radiative
decay. To reduce the phosphorescence quenching, an interlayer has Fig. 21. (a) Device structure, (b) EL efciencies, and (c) EL spectra at different
to be introduced between uorophor and phosphor. In the case of luminance of the designed hybrid WOLEDs (from Ref. [186]).
T1,f > T1,p, the triplet excitons in phosphors cannot be quenched by
uorophors, on the contrary, the triplet excitons in uorophors can the EQE decreases slightly to 10.8% at 500 cd m
2. The EL spectra at
be harvested for emitting-light by transferring them to phosphors. different luminance are shown in Fig. 20b, it is clearly seen that the
This triplet-harvesting from blue uorophor has the potential to devices emitted excellent white light with red, green and blue
achieve nearly 100% exciton utilization efciency in hybrid three emissive peaks, respectively, from CBP: PQIr, CBP: Ir(ppy)3,
WOLEDs. This indicates that the triplet state of blue uorophor and CBP: BCzVBi.
is a key point in the design of high-performance multi-EML hybrid Fig. 20c illustrates the two parallel channels for triplet and
WOLEDs. singlet exciton formation and transfer processes in the EMLs of
above designed hybrid WOLEDs. The majority of excitons are
5.3.1. Hybrid WOLED architectures with interlayer formed in the host material with a singlet-to-triplet exciton
Forrest et al. designed an efcient multi-EML hybrid WOLED by formation ratio of 1:3. The singlet excitons in the two formation
placing an interlayer between uorescent and phosphorescent regions at each side of the EML are efciently transferred to the
EMLs [142]. Fig. 20 shows the device structure and the EL blue uorescent molecules located in these regions. The phosphor-
performance of the resulting WOLED. In this device, CBP was used doped region is located in the center of the EML and separated from
as the interlayer and host, CBP: BCzVBi as the uorescent blue EML, the exciton formation zones by the used interlayer of pure host
and CBP: Ir(ppy)3 and CBP: PQIr as the green and red phosphores- material. The triplet excitons can diffuse to the central region,
cent EMLs, respectively. As given in Fig. 20a, the resulting hybrid where they transfer to the lower-lying energy green and red
WOLEDs show the forward-viewing peak EQE and PE of 11.0% and phosphors. The diffusion of singlet excitons to phosphor dopants is
22.1 lm W
1, respectively, at the current density of 1 mA cm
2, and negligible because of their intrinsically short diffusion lengths
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
[123]. By regulating the EML congurations and precisely
manipulating the generated excitons, the undesirable mutual
exciton quenching has been reduced by inserting the interlayer. It
can be seen that the efciency of the present WOLEDs can be
further improved by using more efcient uorescent dopants.
Fig. 21 shows anther designed hybrid WOLED with an interlayer
[186]. In this device, bis[2-(2-hydroxy-phenyl)-pyridine]beryllium
(Bepp2) is used as the blue uorescent emitter and the host of
green phosphorescent Ir(ppy)2(acac), the mixture of TCTA: Bepp2 is
utilized as the interlayer, and the Ir(MDQ)2(acac) doped into TCTA
as the red phosphorescent EML. To get both blue uorescent and
green phosphorescent emissions, the doping concentration of Ir
(ppy)2(acac) in Bepp2: Ir(ppy)2(acac) layer must be precisely
controlled. The doping concentration of green phosphorescent
emitter is kept as low as 0.3 wt%. Owing to the hole-transporting
property of TCTA and the electron-transporting property of Bepp2,
the injected holes and electrons meet in the TCTA: Bepp2
interlayer, forming the singlet and triplet excitons, then the
created excitons can diffuse to the lower-lying triplet energy red
emissive zone and blue/green emissive zone for being utilized.
Meanwhile, the bipolar transport property of TCTA: Bepp2
interlayer also leads the partial electrons into the red emissive
zone to combine with the holes, and the partial holes into the green
emissive zone to combine with the electrons in this layer, greatly
broadening the recombination zone width. It can be seen that the
resulting hybrid WOLEDs exhibited the maximum CE, PE, and EQE
of 29.4 cd A
1, 34.2 lm W
1, and 13.8%, respectively, and they still
remain 25.4 cd A
1, 23.0 lm W
1, and 11.9% at the practical
brightness of 1000 cd m
2. Moreover, they achieved a rather high
CRI of 90 and kept stable spectral emission with CIE coordinates of
(0.42, 0.44) (Fig. 21b and c). The good device performance should
attribute to the effective and stable manipulation of the formed
excitons in the emissive regions. Furthermore, it is expected that
the efciency of the hybrid WOLEDs designed above should be able
to be further enhanced by using more efcient blue emitters
instead of the Bepp2 blue emitter.
It is well-known that 4P-NPD is a very good blue uorophor
with high quantum yield (92%) and triplet energy (2.3 eV). Ma et al.
designed an efcient multi-EML hybrid WOLED using 4P-NPD as
the blue emitter [187]. The device structure and proposed energy
level diagram are shown in Fig. 22. To prevent the back energy
transfer from the triplet excitons of Ir(ppy)3 (T1 = 2.4 eV) to the
Fig. 22. Energy level scheme for materials used in the hybrid WOLEDs, and exciton (S0, S1, and T1) energy diagram of the emitter layers. R, G, B, and Tm represent Ir
(MDQ)2(acac), Ir(ppy)2(acac), 4P-NPD, and TmPyPb, respectively (from Ref. [187]).
25
non-radiative triplet state of 4P-NPD (T1 = 2.3 eV), CBP: Ir
(MDQ)2(acac) as the red EML is used to separate the mismatched
green and blue EMLs. From the relationship of triplet energy levels,
it is obvious that the triplet excitons on 4P-NPD can be well-
harvested by Ir(MDQ)2(acac) molecules. The singlet excitons of 4P-
NPD can be transferred via a Frster energy transfer process, or
diffuse to the red EML for being utilized. Considering that the
singlet exciton has a shorter exciton diffusion length, it provides a
possibility to separate them spatially. Thus, the red EML should be
located at the distance between the singlet exciton diffusion length
and the triplet exciton diffusion length. On one hand, it allows
sufcient blue emission by regulating the blue EML thickness. On
the other hand, the non-radiative triplet excitons on 4P-NPD can be
diffused to CBP: Ir(MDQ)2(acac) layer for the red emission.
Therefore, all triplet excitons on 4P-NPD molecules are transferred
to the triplet energy of red phosphor Ir(MDQ)2(acac), while
exclusively maintaining the singlet energy on the blue uoro-
phores. Overall, all the generated excitons are consumed for the
white emission. The singlet excitons generated on the blue
uorophores can be used for the blue emission, and the triplet
excitons are utilized for the phosphorescent emission, achieving
the nearly 100% exciton utilization efciency. Accordingly, the
resulting WOLEDs exhibit impressive EL performances with a turn-
on voltage of 3.3 V (see Fig. 23). A forward-viewing maximum EQE
of 21.2% is achieved and remains at 20.0% at 1000 cd m
2, the
maximum PE and CE of 40.7 lm W
1 and 49.6 cd A
1, and then
decrease slightly to 37.1 lm W
1, and 49.5 cd A
1, respectively, with
a CRI of 85 at the luminance of 1000 cd m
2.
To further illustrate the exciton manipulation concept and
improve the CRI of hybrid WOLEDs, a high-performance four-color
hybrid WOLED was constructed [188]. The device structure and
energy transfer diagram are depicted in Fig. 24. Due to the hole-
transporting property of TCTA and the electron-transporting
property of TmPyPb, the injected holes and electrons would meet
in the blue emissive region, forming the exciton recombination
zone, and then the excitons transfer to the adjacent orange EMLs
with low-lying triplet energy level, then sequentially harvested by
the red emitters, forming a cascade energy transfer structure. In
order to avoid the exciton quenching by the higher triplet state-
green emitters (2.4 eV), an interlayer was placed between the blue
EML and the green EML, whose thickness (4 nm) is controlled
larger than the singlet diffusion length and smaller than the triplet
26 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 23. (a) Current density-luminance-voltage characteristics with luminance measured in forward direction without using out-coupling enhancement techniques. The inset
shows the components of the EMLs. (b) External quantum efciency and power efciency versus luminance characteristics of the optimized device. (c) Normalized EL spectra
at different brightness levels (from Ref. [187]).
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 27

Fig. 24. (a) Energy level diagram of used materials and energy transfer diagram in the hybrid WOLEDs. The gray lled rectangle represents the main exciton generation zone.
R, Y, G, B, and Tm represent Ir(piq)3, Ir(bt)2(acac), Ir(ppy)2(acac), 4P-NPD, and TmPyPb, respectively. (b) Device structure of the WOLED. (c) EL spectra of the WOLED at various
brightness levels (from Ref. [188]).

diffusion length. Thus, the generated triplet excitons on TmPyPb
molecules can be transferred to the green emitter molecules.
Overall, with such a working mechanism, all electrically generated
single and triplet excitons can be harvested, realizing nearly 100%
exciton utilization efciency. By the judicious device design and
precisely manipulating excitons, the resulting WOLED achieves
excellent EL performances with the EQE, CE, and PE of 14.2%,
26.0 cd A
1, and 21.9 lm W
1, respectively, at the brightness of
1000 cd m
2. Furthermore, the balanced white spectrum shows a
CRI of 94 over a wide brightness range, which can meet the strict
requirement in museum, studio, art gallery, medical, and wide-
color-gamut display and so on.
5.3.2. Hybrid WOLED architectures without interlayer
Although the inserted interlayer plays an important role in
hybrid WOLEDs, the utilization of interlayer has also several
disadvantages. First, the voltage drop across the interlayer is not
negligible, leading to the reduction of device PE. Second, the
interlayer brings additional interfaces, which on one hand
inevitably increase the possibility of exciplex formation, impairing
the device efciency, on the other hand degrade the device lifetime
due to the interface instability. Third, the transfer of the triplet
exciton energies across the interlayer will also produce additional
losses, thus further decreasing the device efciency. Furthermore,
the introduction of interlayer complicates the device processing,
which is also undesirable for WOLEDs in the future commercial
applications.
Actually, the problems caused by the interlayer in hybrid
WOLEDs can be avoided by using a blue uorophor with higher
triplet energy level than that of used phosphors [55]. However, as
we know, high efciency blue uorophors with high triplet energy
level are few now. Ma et al. designed a novel EML structure to
construct multi-EML hybrid WOLEDs without using an interlayer
[189]. The more importance is that the fabricated hybrid WOLEDs
emit yet higher efciency even though using blue uorophors with
lower triplet energy levels than that of used phosphors as blue
28 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 25. (a) Energy level diagram of used materials and energy transfer diagram in the hybrid WOLEDs. The gray lled rectangle represents the main exciton generation zone.
R, G, B, and Tm represent Ir(MDQ)2(acac), Ir(ppy)2(acac), 4P-NPD, and TmPyPb, respectively (from Ref. [189]).

emitter. The core of design concept in above hybrid WOLEDs is to
introduce mixed hosts with bipolar-transport property to con-
struct the blue uorescent EML, as shown in Fig. 25. The main
exciton generation zone of the device with the mixed hosts TCTA:
TmPyPb should be located across the whole blue EML where the
majority of injected holes and electrons meet with each other. The
generated singlet excitons in the blue EML can undergo the
radiative decay for the blue emission, or be transferred to the
adjacent TCTA: Ir(ppy)2(acac) layer for being harvested via a
Frster energy transfer process. Although this Frster transfer is
not a loss mechanism for light generation, it would lead to the
insufcient blue emission which is required for the balanced white
light. The negative inuence of Dexter-type energy transfer that
favors the formation of the nonradiative triplet excitons on 4P-NPD
can be minimized by decreasing the 4P-NPD doping concentration.
But the presence of Ir(ppy)2(acac) perturbing the utilization of the
singlet excitons for blue emission have a negative effect on the
white light emission when the concentration of 4P-NPD is low. In
order to address these issues, as we designed, the mixture of TCTA
and TmPyPb with the bipolar-transporting property in the blue
EML was employed. The optimized device exhibits impressive EL
performances with a turn-on voltage of 3.1 V. The maximum EQE,
CE, and PE of the device are 19.0%, 45.2 cd A
1, and 41.7 lm W
1,
respectively. The EL spectra of the hybrid WOLED turn out to be
stable within the investigated brightness ranges. Furthermore, the
device can also give off white light with a CRI of 82. Furthermore, at
the practical brightness of 1000 cd m
2, they yet remain 17.0%,
40.5 cd A
1, and 34.3 lm W
1, exhibiting less pronounced efciency
roll-off, which is attributed to the broad exciton recombination
zone within the EML owing to the bipolar-transporting property of
the mixture of TCTA and TmPyPb. Besides, when replacing 4P-NPD
with another uorescent blue emitter 4,40 -bis[2-{4-(N,N-diphe-
nylamino)phenyl}vinyl]biphenyl (DPAVBi) with an extremely low
triplet energy level (< 2.0 eV) in the blue EML, the fabricated
WOLEDs based on the same architecture also exhibited a PE as high
as 40.3 lm W
1 even though the lower PL quantum efciency of
DPAVBi, which is still much better than other conventional multi-
EML hybrid WOLEDs, indicating the universality of this novel
design concept in the realization of high-performance hybrid
WOLEDs.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
5.4. Remaining challenges and prospects
Although the reported hybrid WOLEDs realized the impressive
efciencies, these efciencies are still unsatisfactory compared to
those of the state-of-the-art all phosphorescent WOLEDs. There
exist some challenges to be addressed yet.
First, the absence of efcient and stable blue uorophors with
high triplet state energy level seriously impedes the development
of high-performance hybrid WOLEDs, where the reverse energy
transfer from the phosphorescent emitters to the low-lying triplet
state uorescent emitters signicantly quenches the excitons.
Therefore, the utilization of more efcient blue uorescent
emitters with high T1 and high quantum efciency is obviously
imperative for the development of high performance multi-EML
hybrid WOLEDs.
Another challenge is that the efciency roll-off at higher
luminance is still severe, which has been attributed to the exciton-
exiciton and exciton-polaron quenching. Designing suitable device
structures and selecting matched materials show very important
for the reduction of the quenching, which will be discussed in
detail as follows.
Considering the future commercial applications, the cost could
be another challenge for the hybrid WOLEDs before they can
become applied for solid-state lighting. Most of the efcient hybrid
WOLEDs have generally rather complicated structures and
fabricated by the vacuum evaporation technology, leading to high
fabrication costs.
To solve the issues mentioned above, a recent breakthrough on
the development of TADF materials makes the more efcient blue
uorophores with high T1 feasible [85]. Because the generated
triplet excitons can be harvested by a RISC process induced by
sufciently small DEST, thus the TADF materials can achieve 100%
exciton utilization efciency as the alternative of phosphorescent
emitters. Nowadays, the highly efcient blue TADF materials with
high T1 and PLQY have been successfully synthesized, providing
another selection in materials for the fabrication of high
performance WOLEDs
Fig. 26. Chemical structures of synthesized blue TADF molecules. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version
of this article.)
29
6. WOLEDs with TADF emitters and phosphors
6.1. Thermally activated delayed uorescence (TADF)
Recent studies have been focusing on the TADF in order to
develop highly efcient blue uorescent materials. Adachi et al.
studied various simple aromatic compounds with high PL
efciency and efcient TADF effect to obtain high EL efciency.
Higher efciency than the limited EQE (5%) of conventional
uorescent materials was accomplished by up-converting the
formed triplet excitons to singlet excitons for emission. As known,
in order to achieve this, the spin-forbidden triplet excitons must be
converted to the singlet level through a RISC process, thus the
design molecules must have very small DEST value. In the aspect of
blue TADF materials, some good material systems have been
successfully synthesized [85,79,190192], as shown in Fig. 26. The
maximum EQE of the fabricated blue OLEDs based on synthesized
TADF materials have been over 19.5%.
6.2. S-EML WOLEDs based on blue TADF materials
6.2.1. Single-molecule TADF systems
These blue TADF molecules can be used to construct high-
efciency hybrid WOLEDs. Fig. 27 shows the schematic diagrams
for the management of singlet and triplet excitons in S-EML hybrid
WOLEDs using conventional uorophors and blue TADF molecules
as host, respectively. For the case of conventional uorophors as
host (Fig. 27a), in Zone I (green circle coverage), the excitons
created on the blue host including singlet and triplet excitons can
be efciently transferred to the phosphorescent dopant, leading to
a theoretical IQE of 100% but only emission from the phosphores-
cent dopants. In Zone II (pink circle coverage), the triplet excitons
on the host can be transferred to the dopant, and the blue emission
from the host and phosphorescent emission from dopant can be
obtained with a theoretical IQE of 100%. In Zone III (uncovered
zone), no excitons on the host can be transferred to the dopant
molecules, which will only give off blue emission with a theoretical
IQE of 25%. As seen, a suitable portion of Zone III is essential for
maintaining the balanced white light, but it gives an IQE lower than
100%. To address this problem, using the efcient blue TADF
emitters instead of the conventional blue uorophors seems an
effective approach. For the hybrid WOLEDs using the blue TADF
30 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 27. Schematic diagrams for management of singlet and triplet excitons in single-EML hybrid WOLEDs based on a) conventional blue uorophors and b) TADF blue
emitters with low doping concentrations. Green circle coverage represents diffusion zone of singlet excitons, namely Zone I. Pink circle coverage represents diffusion zone of
triplet excitons, namely Zone II. The uncovered zone is Zone III. RS and RT are respectively diffusion lengths of singlet and triplet excitons; compared with conventional host, RT
of TADF host is smaller due to the fast competition process of RISC. F represents uorescence; P is phosphorescence, Nr is nonradiative decay; ISC is intersystem crossing, RISC
is reverse intersystem crossing, and IQE is the internal quantum efciency (from Ref. [194]). (For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)

emitters as host, both the singlet and triplet excitons in Zone III
now can be harvested for the blue emission with a theoretical 100%
IQE due to the energy transfer of the triplet excitons to the singlet
excitons by reverse intersystem crossing. Accordingly, a TADF host-
phosphor dopant WOLED can simultaneously achieve 100% IQE
and white light emission by controlling the phosphor dopant at a
low doping concentration.
Duan et al. fabricated a simplied S-EML hybrid WOLED using
DMAC-DPS TADF molecule as host and blue emitter, (acetylace-
tonato)bis[2-(thieno[3,2-c] pyridin-4-yl)phenyl]iridium(III) (PO-
01) as an orange phosphorescent emitter [193]. Fig. 28 shows the
device structure and the energy transfer diagram of the resulting
hybrid WOLEDs. For the generated singlet excitons on DPEPO, they
are either used to give off the blue emission, or converted into its
triplet through ISC and transferred to the dopant, which can be
regulated by varying the dopant concentration of PO-01. While, for
the generated triplet excitons on DMAC-DSP, because the dopant
concentration can be controlled very low, the direct Dexter energy
transfer can be neglected. Like the most conventional uorophores,
the triplet excitons can be diffused to the host molecules around
the dopant and then be transferred through Dexter transfer. Due to
the small energy gap between its singlet state and triplet state, the
triplet exciton on the host can be efciently up-converted into its
singlet state, from where the energy can be transferred through the
long-range interaction. The long-range energy transfer can
eliminate the triplet loss during the exciton diffusion process,
enhancing the energy transfer from host triplet to dopant. The
singlet excitons up-converted from the triplet state of the host,
either utilized by the blue emitters or transferred to the dopant
molecules, can minimize the triplet density at the high current
density, which is benecial to decrease the efciency roll-off in
WOLEDs. By the precise exciton manipulation concept described
above, the resulting hybrid WOLEDs exhibited high EQE and PE of
20.8% and 51.2 lm W
1, respectively, with CIE coordinates of (0.398,
0.456) at the luminance of 500 cd m
2.
6.2.2. TADF exciplex systems
In addition to the utilization of single-molecule TADF materials
as the host, the exciplex with TADF effect has recently drawn
substantial attention [97]. Lee et al. reported an efcient TADF
exciplex system formed by 1:1 mixing a hole-transporting
molecule 4,40 -bis(9-carbazolyl)-2,20 -dimethylbiphenyl (CDBP)
and an electron-transporting molecule ((1,3,5-triazine-2,4,6-
triyl)tris(benzene-3,1-diyl)) tris(diphenylphosphine oxide) (PO-
T2T) [194], as shown in Fig. 29. Both CDBP and PO-T2 T have PL
emission peaks smaller than 400 nm, whereas the CDBP: PO-T2 T
mixed lm shows a broad and signicantly red-shifted PL
spectrum with regard to those of the pristine lms. The CDBP:
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 31

Fig. 28. (a) Proposed energy diagram of the hybrid WOLEDs with blue TADF as host and molecule structures. (b) Energy transfer diagram from the blue TADF host emitter to
the orange phosphor (from Ref. [193]). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
 32 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 29. (a) Molecular structures of CDBP and PO-T2T. (b) UV-vis absorption and photoluminescence (PL) spectra of CDBP, PO-T2 T and CDBP: PO-T2 T in deposited lms. (c)
Phosphorescence spectra of CDBP and PO-T2 T in 2-MeTHF and uorescence and phosphorescence spectra of CDBP: PO-T2 T in solid-state lm at 77 K (from Ref. [194]).

PO-T2 T mixed lm emits a peak at 476 nm, indicating that the
CDBP: PO-T2 T mixed lm forms exciplex emission. According to
the PL decays, the CDBP: PO-T2 T mixed lm has two longer decay
times, 27.2 ns and 1.7 ms. The relatively short decay time of 27.2 ns
should be attributed to the prompt uorescence of CDBP: PO-T2 T
exciplex rather than the individual CDBP and PO-T2T. The long
decay time of 1.7 ms should then be assigned to the delayed
uorescence of CDBP: PO-T2 T exciplex. The temperature-depen-
dent transient PL decay measurements further demonstrate that
the delayed component is due to the TADF. Thus, by doping green
(Ir(ppy)2(acac))/red (Ir(MDQ)2(acac)) phosphors into the blue
TADF exciplex system, they fabricated an S-EML hybrid WOLED,
as the EL spectra shown Fig. 30. The resulting WOLEDs exhibited
the maximum EQE, CE, and PE of 25.5%, 67.0 cd A
1, 84.1 lm W
1,
respectively. Although the device achieved good maximum
efciencies, they decreased to 14.8%, 37.0 cd A
1, and 24.2 lm W
1,
at 1000 cd m
2, exhibiting severe efciency roll-off, and the EL
spectra showed obvious color-shift with the increased luminance
with a CRI of 76, which should be resolved in future work.

6.3. Multi-EML WOLEDs based on blue TADF materials

6.3.1. Complementary color architectures

Fig. 30. EL spectra and CRI values of the hybrid WOLEDs based on TADF exciplex
host at different luminance (from Ref. [194]).
Besides S-EML hybrid WOLEDs, multi-EML hybrid WOLEDs
based on blue TADF materials have also been successfully
fabricated, which can resolve the existed problems in S-EML
hybrid WOLEDs. Fig. 31 shows the complementary-color dual-EML
hybrid WOLEDs using TADF 2CzPN as the blue emitter and PO-01 as
the orange phosphorescent emitter [195]. The two emitters were
separately doped into different hosts, forming double EMLs. By
employing the TADF material as the blue uorophor, on one hand,
this design structure can eliminate the interlayer between
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 33

Fig. 31. Energy level scheme for materials used in the hybrid WOLED, and exciton (S0, S1, and T1) energy diagram of the emitting layers. The gray lled rectangle represents the
main exciton generation zone. Solid lines and dashed lines correspond to HOMO and LUMO energy levels, respectively; circles and diamonds refer to HOMO and LUMO exciton
energies, respectively. PF is the prompt uorescence while DF is the delayed uorescence. ISC denotes the intersystem crossing, RISC indicates the reverse ISC, and ET denotes
the energy transfer (from Ref. [195]).

Fig. 32. (a) Transient decay curves of devices with or without interlayer observed at 480 nm. (b) Transient decay curves of devices with or without interlayer observed at
560 nm (from Ref. [195]).

uorescent and phosphorescent emissive regions. On the other
hand, it can effectively suppress the intrinsically mutual quenching
between uorescent emitter and phosphorescent emitter even
though without the interlayer. The transient EL measurement was
carried out to study the operational mechanism of the resulting
WOLEDs, as shown in Fig. 32. The transient decay curves observed
at 480 nm show the prompt parts and the delayed parts, which are
an inherent feature of the TADF process, indicating that the TADF
process happens in 2CzPN. The triplet excitons are used by the blue
uorophor. In addition, in turn-off region, the overshoots were
observed, which demonstrates the charge trapping on 2CzPN, the
electrons at mCP/TAZ interface can be injected into the mCP HOMO
level and can then be trapped by 2CzPN owing to its low-lying
LUMO level. Besides, because the small charges are directly
34 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

Fig. 33. Proposed energy level diagram of the TADF-based hybrid WOLEDs and chemical structures of the used emitter dopants. R, G and B represent Ir(PPQ)2(acac), Ir
(ppy)2(acac) and DMAC-DPS, respectively. Solid lines and dashed lines refer to HOMO and LUMO energy levels; circles and diamonds correspond to the exciton energies (S0, S1
and T1), respectively. presents the energy transfer process and is the carrier trapping process. PF is the prompt uorescence, DF is the delayed uorescence. ISC denotes the
intersystem crossing, RISC indicates the reverse ISC (from Ref. [196]).

injected into mCP, with respect to the device without interlayer,
the overshoot is much lower in the device with mCP interlayer.
Furthermore, compared with the transient decay curve of device
with an EML of mCP: 4% PO-01, those of the WOLEDs observed at
560 nm show the delayed components, evidencing that the energy
transfer from 2CzPN to PO-01 occurs. The energy transfer prolongs
the lifetime of the decay curves of PO-01 due to the long lifetime of
the delay part of 2CzPN. By taking advantage of the energy levels of
the materials and the trapping ability of the dopant, the resulting
WOLEDs achieved a maximum forward-viewing EQE of 22.5% and
PE of 47.6 lm W
1 with CIE coordinates of (0.45, 0.49).
6.3.2. Primary colors architectures
As shown, although some TADF-based hybrid WOLEDs achieved
an impressive EL efciency, the problems are still obvious in severe
efciency roll-off, poor color stability and low CRI. The realization
of simultaneous high efciency, superior color stability, high CRI,
and low efciency roll-off in TADF-based hybrid WOLEDs remains a
big challenge.
Recently, Ma et al. demonstrated high-performance TADF-
based hybrid WOLEDs employing TADF molecule DMAC-DPS as the
blue emitter combined with red and green phosphorescent
emitters [196]. Fig. 33 shows the device structure and the
operational mechanism of the designed hybrid WOLEDs. Due to
the high triplet state energy of DMAC-DPS, the triplet excitons
generated in the blue emissive region can be transferred to the
adjacent low-lying green phosphorescent molecules, and sequen-
tially transferred to the red phosphorescent ones, forming a
cascaded energy transfer structure. For the singlet excitons, they
can either decay for the blue emission, or be transferred to
phosphorescent layers.
Overall, all the generated singlet and triplet excitons can be
effectively utilized for the radiative decay, realizing 100% exciton
utilization efciency. Meanwhile, it can be found that the EL
performance of the resulting WOLEDs is dependent the doping
concentration of Ir(ppy)2(acac), therefore, judicious concentration
regulation makes us to obtain balanced white light and high device
performance. Clearly, by the utilization of blue-green-red cascade
energy transfer structure, the judicious regulation of doping
concentration, and the precise manipulation of charges and
excitons, the resulting hybrid WOLEDs show excellent EL efcien-
cies with the forward-viewing maximum EQE, CE, and PE of 23.0%,
51.0 cd A
1, and 51.7 lm W
1, respectively, which are even compa-
rable to those of the state-of-the-art all phosphorescent WOLEDs.
Moreover, the EL spectra exhibit remarkable color stability with a
high CRI of 89, CIE coordinates of (0.438, 0.438) and a CCT of 3231 K
at the brightness of 1000 cd m
2, as shown in Fig. 34.
6.4. Remaining challenges and prospects
We have reviewed the recent advances of hybrid WOLEDs using
blue TADF molecules as the uorescent dopant emitter. Obviously,
the overall EL performances can surpass those of the hybrid
WOLEDs with conventional uorescent emitters, and even be
comparable to those of all phosphorescent WOLEDs. Even so, the
WOLEDs using TADF as the emitters still suffer from some big
challenges.
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142 35

Fig. 34. (a) Current density-luminance voltage characteristics of the designed TADF-based WOLEDs, with luminance measured in forward-viewing direction without any
out-coupling enhancement techniques. The inset shows the structure of EMLs. (b) External quantum efciency and power efciency versus luminance characteristics of the
device. The inset denotes the normalized EL spectra at different brightness levels (from Ref. [196]).

As we see, the reported blue TADF molecules usually exhibited
wide emission spectra (80120 nm for the full width at half
maxima) [197]. Although the broad spectra coverage in the blue
region can benet for the CRI improvement in WOLEDs, it also
affects the color purity of blue emitters. Moreover, the true-blue
TADF molecules have been very rare to date. Thus, deep-blue TADF
molecules with good color purity are valuable to be further
studied.
Further challenge in TADF-based WOLEDs is the efciency roll-
off at higher luminance, which might be the most urgent problem
to be solved nowadays. Due to the inherent long delayed lifetime of
TADF molecules, the probability of the exciton quenching
processes such as STA, TTA, and exciton-polaron quenching are
increasing with the increase of luminance. Much work in device
engineering and selecting matched material systems will be
further made to mitigate the efciency roll-off in TADF-based
OLEDs.
Of course, lifetime is also a problem. As previously reported,
when the famous blue TADF emitter DMAC-DPS is applied into
OLEDs, the blue device lifetime is unsatised, less than one hour.
Suitable matched host materials and stable TADF molecules still
need to be further investigated.
36 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 35. Proposed energy diagrams of exciton-conned structure all phosphorescent WOLEDs and chemical structures of the used materials (from Ref. [56]).
7. Reducing efciency roll-off at high luminance
From the previous discussions, it can be seen that the efciency
roll-off at high luminance is obvious in most all phosphorescent
and uorescence/phosphorescence hybrid WOLEDs, which has
become one of the most urgent challenges to be solved. Much
endeavor has been made in attempt to enhance the high-
brightness performance. In this section, we review the effective
strategies by device engineering to reduce the efciency roll-off at
high luminance, including an effective conned structure,
decreasing the exciton lifetime, reducing the molecule aggregation
as well as broadening the exciton recombination zone by judicious
device design.
7.1. Effective charge and exciton-conned structures
As known, triplet exciton generally has a long diffusion length.
The effective connement of excitons within EMLs can be achieved
when all corresponding materials, i.e., host materials, adjacent
hole-transporting material and electron-transporting material,
have higher triplet energy level than that of the dopant emitters.
And the effective charge-connement can be realized by using the
hole- and electron- blocking materials with deeper HOMO for
holes and shallower LUMO for electrons.
Kido et al. reported an exciton-conned structure all phospho-
rescent WOLEDs with the EML of DCzPPy: 20% FIrpic (4.75 nm)/
DCzPPy: 3% PQ2Ir (0.25 nm)/TCTA: 3% PQ2Ir (0.25 nm)/TCTA: 7%
FIrpic (4.75 nm) [56], the energy diagram was shown in Fig. 35.
This structure made the generated triplet excitons to conne
within the 10 nm-thickness EML. Because the LUMO level of
3DTAPBP is 0.30 and 1.34 eV higher than those of TCTA and FIrpic,
respectively, conning the electrons within the emissive layers. In
addition, the HOMO level of BmPyPB is 0.62 and 0.52 eV deeper
than those of DCzPPy and FIrpic, respectively, conning the holes
within the emissive layers. Moreover, the introduction of the D-
EML limits the triplet exciton diffusion, thus reducing the
possibility of triplet-polaron quenching, and thus mitigating the
efciency roll-off. The resulting device showed a power efciency
of 53 lm W
1 at the display luminance of 100 cd m
2, and rolls off
to 44 lm W
1 at a practical brightness of 1000 cd m
2. Although
this device structure cannot broaden the exciton recombination
zone, it can effectively conne the generated excitons within the
EML well, which will greatly avoid the quenching by the massive
polarons, thus mitigating the efciency roll-off.
Fig. 36 shows another designed device structure that can well
improve efciency roll-off in all phosphorescent OLEDs, an
efcient sandwich-type EML structure with a mixed-host EML
sandwiched between two single-host EMLs [198]. On one hand, the
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 36. Device structure of the designed OLEDs based on an efcient sandwich-type EML structure with a mixed-host EML sandwiched between two single-host EMLs (from
Ref. [198]).
two single-host EMLs in the sandwich-type EML architecture can
strongly conne the excitons inside of the EML away from the
interface between the emissive layer and the blocking layer. On the
other hand, they can effectively harness the diffused excitons from
the main exciton recombination zone and broaden the recombi-
nation zone. According to the analysis of exciton-density driven
quenching mechanism models, it is found that the TTA is dominant
in the device with the sandwich-type emissive structure. It can be
seen that the sandwich-type emissive structure can be used to
effectively utilize all the electrically generated both triplet and
singlet excitons to obtain high efciency and low efciency roll-off
in OLEDs. Compared with the conventional EML structures such as
S-EML, D-EML, and M-EML, the devices with the proposed
sandwich-type EML exhibits reduced efciency roll-off and
improved device lifetime. Obviously, it can be anticipated that
WOLEDs based on the sandwich-type EML structure must be able
to achieve high efciency, low efciency roll-off and good stability
simultaneously.
7.2. Decreasing exciton lifetime
In general, the exciton density in OLEDs strongly depends on the
exciton lifetime. For OLEDs based on uorescent materials, which
typically have a singlet exciton lifetime in the nanosecond regime,
37
the singlet densities are around 1014 cm
3 at 100 mA cm
2. Such
singlet densities are too low to cause signicant efciency roll-off.
The observed efciency roll-off is usually attributed to the high
triplet and polaron densities. Therefore, decreasing the radiative
exciton lifetime is most relevant to the phosphorescent materials
and devices.
For the TADF molecule 2CzPN, the exciton delay lifetime is as
long as 100 ms, while the exciton lifetime for DMAC-DPS is
decreased to 3 ms, it can be seen that the DMAC-DPS-based blue
OLEDs exhibit lower efciency roll-off compared to the counter-
parts based on 2CzPN. Even so, the exciton delay lifetime is still
three orders of magnitude above the singlet lifetime of uorescent
emitter. Thus, the TADF emitters-based WOLEDs generally suffer
from the severe efciency roll-off at high luminance, which can be
attributed to the long delay lifetime of excitons. Instead of using
the TADF molecules, high-efciency uorescent WOLEDs with low
efciency roll-off employing DMAC-DPS as the host combined with
the conventional uorescent emitters have been demonstrated
[199]. Fig. 37 exhibited the device structure and EL performance of
the resulting WOLEDs. By combination of a TADF molecule and a
conventional uorescent emitter, namely, DMAC-DPS for blue
emission and 2,8-ditert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-
diphenyltetracene (TBRb) for orange emission, high-efciency all
uorescent WOLEDs are achieved. In the devices, the singlet
38 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 37. (a) Device structure, (b) Energy level diagram, (c) EL performance of the resulting WOLEDs (from Ref. [199]).
excitons created in the TADF host or assistant dopant are directly
transferred into the singlet state of the uorescent emitters by an
efcient FRET process. Meanwhile, the generated triplet excitons
on TADF molecules can be up-converted into its singlet states and
then transfer into the singlet state of the emitters, or they may be
transferred to the T1 of the emitter by a Dexter energy transfer
(DXET) process, which is a short-range energy transfer and can be
effectively blocked by increasing the distance between the donor
and the acceptor. Because the DXET process can lead to the energy
loss in the uorescent WOLEDs, we can regulate the concentration
of the dopant emitter to prevent from the DXET process.
Accordingly, the resulting WOLEDs using DMAC-DPS as the host
exhibit excellent EL performances with the maximum forward-
viewing PE, CE, and EQE of 48.0 lm W
1, 45.1 cd A
1, and 14.0%,
respectively. At a practical brightness of 1000 cd m
2, they remain
as high as 29.3 lm W
1, 42.0 cd A
1, and 13.0%, respectively, with
CIE coordinate of (0.38, 0.49), indicating very low efciency roll-off
compared with the TADF emitters-based WOLEDs.
7.3. Reducing molecular aggregation
The molecular aggregation usually describes molecular cluster-
ing rather than the formation of physical dimers, resulting in the
severe Dexter-based TTA. To minimize this process, the average
distance between emitter molecules should be as large as possible,
and thus aggregation in particular needs to be avoided. To achieve
this, both molecular design approaches and customizing stack
design have been pursued. One way to increase the average
intermolecular distance of emitter molecules and thus to reduce
Dexter-based TTA rates is the introduction of large dendrons into
uorescent or phosphorescent complexes [200,201].
Reineke et al. divided the EML into six alternating layers of 1 nm
TCTA: Ir(ppy)3 followed by a 2 nm thick un-doped TCTA interlayer
[118], as shown in Fig. 38. In this case, kTT decreased by a factor of 2
compared with the reference device with a single TCTA: Ir(ppy)3
layer, and OLEDs based on such EMLs show an improved roll-off
behavior. As seen, reducing the molecular aggregation can
signicantly decrease the efciency roll-off in phosphorescent
OLEDs. Thus, to achieve high-efciency WOLEDs with reduced
 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142
Fig. 38. Sub-structuring the EML of an OLED using intrinsic interlayer can prevent
exciton annihilation in one dimension. a) Schematic of the EML: 1 nm thick layers of
TCTA: Ir(ppy)3 (10 mol%) alternate with 2 nm thick intrinsic TCTA intrinsic
interlayers. b) EQE versus current density for the sub-structured device and for an
unstructured reference device with the same EML thickness (from Ref. [116]).
efciency roll-off, the selection of lumophores without tending to
molecular aggregation is one of the key points.
7.4. Broadening exciton recombination zone within EML
The impact of exciton recombination zone in OLEDs on the
efciency roll-off is one of the most relevant factors [202]. Fig. 39
shows the efciency roll-off in gradient-EML devices having
recombination zone widths which vary from 2 to 200 nm. The
increase in thickness to further expand the recombination zone
must be balanced by potential increase in resistance and driving
voltage. It is expected that this optimization will be facilitated by
further engineering the composition gradient in thick layers. In
OLEDs, engineering the recombination zone width, while main-
taining charge and exciton connement, offers a route towards
relieving the efciency roll-off in OLEDs.
In WOLEDs, broadening the exciton recombination zone width
is an effective approach to reduced efciency roll-off. As shown in
Fig. 8, due to the bipolar-transporting property of 26DCzPPy in the
blue emissive region, The TTA and TPQ are signicantly suppressed
by smartly designing the emission zone structure, thus broadening
the recombination width. Besides, within the EML of the blue-
green-red cascaded energy transfer structure, the formed singlet
and triplet excitons in the blue emissive zone can be sequentially
harvested by the green and red emitting-molecules, which can
reduce the exciton loss and the probability of the exciton
quenching processes, as a result, the efciency roll-off in the
devices is greatly improved.
As the WOLEDs shown in Fig. 22, the used CBP, showing a
preferred hole-transporting property, causes an overow of holes
39
Fig. 39. Normalized hEQE for gradient-EML devices with varying recombination
zone widths (from Ref. [202]).
in the blue EML. And the large energy offset (0.8 eV) of HOMO
between CBP and TmPyPb effectively prevents the holes to
transport into the adjacent TmPyPb layer, easily causing excessive
holes to accumulate at the interface between the blue EML and the
HBL, which would impair the device efciency because of TPQ.
However, the large amount of trapped holes on 4P-NPD sites would
reduce the number of accumulated holes at that interface,
alleviating the formation of h+ polarons, and thereby limiting
the quantity of triplet-polaron pairs. Even so, the high concentra-
tion of the trapped holes can further benet for the electron
injection and hence transport via hopping on emitter molecular
sites, which is benecial to electron-hole balance. Obviously, this
exciton generation zone broadening into the green and red EMLs in
the WOLEDs relies on the bipolar transport properties of CBP. It can
be seen that the resulting WOLEDs indeed show good roll-off
property. Similarly, as shown in Fig. 25, the bipolar-transporting
property of TCTA:TmPyPb mixture used in the blue EML broadens
the exciton generation zone, which decreases the local exciton
density and reduce the TTA and TPQ. As we see, the resulting
WOLEDs exhibit less pronounced efciency roll-off at high
luminance.
8. Concluding remarks
WOLEDs have drawn substantial attention in both scientic and
industrial elds during the past decades. Their merits such as high
efciency, low driving voltage, exibility, and low energy
consumption have made them the most promising candidate for
the next-generation full-color displays and solid-state lighting
sources. Practically, much endeavor has been taken to realize high
efciency, high color-quality, device stability, simple and low-cost
fabrication procedure as well as the trade-off among these
parameters for WOLEDs. Thanks to these impressive efforts,
WOLEDs have been obtaining an increasing momentum through
the continued breakthroughs. However, it can be found that
whatever advanced materials and subtle device design architec-
tures we used, the core is always related to manipulating the
generated singlet and triplet excitons that are involved in the
internal physical processes in the devices. In this review, we
illustrated the recent advances in WOLEDs based on this clue. As
seen, the exciton manipulation concept plays a crucial role in
achieving superior efciency/CRI/color stability simultaneously.
Other than the above parameters, the future attention should
be paid to improving the device lifetime and reducing the
efciency roll-off at high luminance in WOLEDs. On the side of
materials selection, TADF emitters seem to be a better solution,
considering their high efciency and high reliability. On the side of
device design, strategies like the utilization of effective charge/
40 Z. Wu, D. Ma / Materials Science and Engineering R 107 (2016) 142

exciton-conned EML structures, cascaded energy transfer struc- (Continued)

tures, bipolar transportation in EML and precise doping concen- Abbreviation Chemical Name Function
tration regulation strategies would be benecial to resolving both
iridium(III)bis(2,4-diphenyl-quinoline) red phos.
issues. (acetylacetonate) emitter
Because of the long operational lifetimes, high color purity, and FIr6 bis(2,4-diuorophenylpyridinato)tetrakis(1- blue phos.
potential to be manufactured at low cost in next-generation pyrazolyl)borate iridium(III) emitter
display and lighting applications, all uorescent WOLEDs are FIrpic bis(3,5-diuoro-2-(2-pyridyl)phenyl-(2- blue phos.
carboxypyridyl)iridium(III) emitter
increasingly attractive. In the forthcoming years, it can be Ir bis(2-methyldibenzo[f,h]quinoxaline) red phos.
anticipated that the TADF-based all uorescent WOLEDs with (MDQ)2(acac) (acetylacetonate)iridium (III) emitter
high efciency, good reliability, and low efciency roll-off would Ir(ppy)3 fac-tris(2-phenylpyridine)iridium(III) green phos.
offer a new avenue to future development of high-performance emitter
0
Ir(ppy)2(acac) bis(2-phenylpyridinato-N,C2 )iridium
WOLEDs.
(acetylacetonate)
o-CzOXD 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4- Host
Acknowledgements oxadiazole
0
PQIr iridium(III)bis(2-phenyl quinolyl-N,C2 ) red phos.
The authors gratefully acknowledge the National Natural acetylacetonate emitter
mCP 1,3-bis(carbazol-9-yl)benzene Host
Science Foundation of China (51333007, 91433201) and the m-MTDATA 4,40 ,4-tris(N-3-methylphenyl-N-phenylamino) HTL
International Cooperation Foundation of China (2015DFG12470) triphenylamine
for the support of this research. mCBP 3,3-di(9H-carbazol-9-yl)biphenyl Host
NPB N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)- HTL + host
benzidine
Appendix A.
SPPO1 9,9-spirobiuoren-2-yl-diphenyl-phosphine host + EBL
oxide
TCTA 4,40 ,4-tris(carbazol-9-yl)-triphenylamine host + HTL
International Union of Pure and Applied Chemistry (IUPAC) names of TAPC 1,10 -bis[4-(di-p-tolylamino)phenyl]cyclohexane HTL
the materials discussed. TTPA 9,10-bis[N,N-di-(p-tolyl)-amino]anthracene green uor.
emitter
TPBi 2,20 ,2-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H- ETL
Abbreviation Chemical Name Function benzimidazole)
Alq3 8-hydroxyquinoline aluminum host + ETL TBRb 2,8-di-tert-butyl-5,11-bis(4-tert-butylphenyl)- orange
B3PYMPM bis-4,6-(3,5-di-3-pyridylphenyl)-2- ETL 6,12-diphenyltetracene uor.
methylpyrimidine emitter
BCP 2,9-dimethyl-4,7-diphenyl-1,10- ETL + EBL UGH2 1,4-bis(triphenylsilyl)benzene Host
phenanthroline DMAC-DPS bis[4-(9,9-dimethyl-9,10-dihydroacridine) blue
4P-NPD N,N'-di-(1-naphthalenyl)-N,N'-diphenyl- blue uor. phenyl]sulfone TADF + host
[1,10 :40 ,1:4,1000 -quaterphenyl]- 4,4000 -diamine emitter DTC-DPS bis[4-(3,6-di-tert
butylcarbazole)phenyl] blue TADF
3TPYMB tris[3-(3-pyridyl)-mesityl] borane ETL sulfone
3DTAPBP 2,20 -bis(m-di-p-tolylaminophenyl)-1,10 - HTL DMOC-DPS bis[4-(3,6-dimethoxycarbazole)phenyl]sulfone blue TADF
biphenyl 2CzPN 4,5-di (9H-carbazol-9-yl) phthalonitrile blue TADF
BmPyPB 1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene ETL CzAcSF 10-(4-((4-(9H-carbazol-9-yl)phenyl)sulfonyl)- blue TADF
Bepp2 bis(2-(2-hydroxyphenyl)-pyridine)beryllium host + ETL phenyl)-9,9-dimethyl-9,10-dihydroacridine
Bebq2 bis(10-hydroxybenzo[h] quinolinato)beryllium host + ETL PIC-TRZ 2-biphenyl-4,6-bis(12-phenylindolo[2,3-a] Sky-blue
complex carbazole-11-yl)-1,3,5-triazine TADF
BczVBi 4,40 -bis(9-ethyl-3-carbazovinylene)-1,10 - blue uor. PXZ-TRX 2-phenoxazine-4,6-diphenyl-1,3,5-triazine green TADF
biphenyl emitter 4CzIPN (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl) green TADF
BPhen 4,7-diphenyl-1,10-phenanthroline ETL isophthalonitrile
CBP 4,40 -bis(carbazol-9-yl)biphenyl Host tri-PXZ-TRZ 2,4,6-tri(4-(10H-phenoxazin-10H-yl)phenyl)- yellow
CDBP 4,40 -bis(carbazol-9-yl)-2,20 -dimethylbiphenyl host + HTL 1,3,5-triazine TADF
CzSi 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)- host + EBL 4CzTPNPh 2,3,5,6-tetrakis(3,6-diphenylcarbazol-9-yl)-1,4- orange
9H-carbazole dicyanobenzene TADF
DCJTB 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7- red uor.
tetramethyljulolidin-4-yl-vinyl)- 4H-pyran emitter
DBP tetraphenyldibenzoperi an-thene red uor.
emitter
DCzPPy 2,6-bis(3-(9H-carbazol-9-yl)phenyl)pyridine Host References
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