FULL PAPER
Quantum Dot LEDs
Over 30% External Quantum Efficiency Light-Emitting
Diodes by Engineering Quantum Dot-Assisted Energy
Level Match for Hole Transport Layer
Jiaojiao Song, Ouyang Wang, Huaibin Shen,* Qingli Lin, Zhaohan Li, Lei Wang,
Xintong Zhang, and Lin Song Li*
In the study of hybrid quantum dot light-emitting diodes (QLEDs), even for
state-of-the-art achievement, there still exists a long-standing charge balance
problem, i.e., sufficient electron injection versus inefficient hole injection
due to the large valence band offset of quantum dots (QDs) with respect to
the adjacent carrier transport layer. Here the dedicated design and synthesis
of high luminescence Zn1−xCdxSe/ZnSe/ZnS QDs is reported by precisely
controlled shell growth, which have matched energy level with the adjacent
hole transport layer in QLEDs. As emitters, such Zn1−xCdxSe- based QLEDs
exhibit peak external quantum efficiencies (EQE) of up to 30.9%, maximum
brightness of over 334 000 cd m−2, very low efficiency roll-off at high current
density (EQE ≈25% @ current density of 150 mA cm−2), and operational
lifetime extended to ≈1 800 000 h at 100 cd m−2. These extraordinary
performances make this work the best among all solution-processed QLEDs
reported in literature so far by achieving simultaneously high luminescence
and balanced charge injection. These major advances are attributed to the
combination of an intermediate ZnSe layer with an ultrathin ZnS outer layer
as the shell materials and surface modification with 2-ethylhexane-1-thiol,
which can dramatically improve hole injection efficiency and thus lead to
more balanced charge injection.
1. Introduction
The high luminescence efficiency, size-controllable emission-
wavelength tunability, and narrow emission linewidth of
solution-processable colloidal quantum dots (QDs) highlight
the potential application of QD-based light-emitting devices
(QLEDs) for next generation display and solid state lighting.[1–7]
Great efforts have been devoted to improving performance
J. Song, O. Wang, Prof. H. Shen, Dr. Q. Lin, Dr. Z. Li, Prof. L. S. Li
Key Laboratory for Special Functional Materials of Ministry of Education
Henan University
Kaifeng 475004, P. R. China
E-mail: shenhuaibin@henu.edu.cn; lsli@henu.edu.cn
L. Wang, Prof. X. Zhang
Key Laboratory of UV-Emitting Materials and Technology
of Ministry of Education
Northeast Normal University
Changchun 130024, P. R. China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201808377.
DOI: 10.1002/adfm.201808377
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of QLEDs to meet the demands in high
energy efficiency and stability of prac-
tical use.[2–6] By adapting high quantum
yield QDs, recent breakthrough of QLEDs
has boosted the brightness to 165 000,[8]
460 000,[3] and 20 900 cd m−2,[9] for red,
green, and blue QLEDs, respectively.
For peak external quantum efficiencies
(EQEs), it have been improved impres-
sively to 20.5%,[2] 24%,[10] and 19.8%[11] in
red, green, and blue QLEDs. And further
by adopting tandem structure, EQEs for
all three colored QLEDs can even exceed
21%.[12] However, the peak EQE is still
lower than the theoretical value of ≈30%
if the effect of light interference between
different layers is taken into account in a
multilayer hybrid organic LED,[13,14] and
the lifetime of QLEDs is far below the
requirement of display or lighting appli-
cations, which was only in the range of
hundreds of thousands of hours with
an initial brightness of 100 cd m−2.[6] To
further maximize EQE, minimize power
consumption and improve lifetime, world-
wide researchers currently put significant efforts into many
attempts on different types of QDs and electroluminescent (EL)
device structures.[3,6,15]
Besides the use of high luminescence QDs, balanced
charge injection in QLEDs is extremely important for the
structure design of ideal devices.[4–6] Since ZnO nanopar-
ticles have been adapted as an efficient electron transport
layer, the relative inefficient hole transport in QLEDs will
cause an imbalance between electrons and holes in the
emitting layer.[4–6] Such drawback impedes the overall per-
formance of QLEDs to be further improved. It is extremely
important to establish a perfect energy level match between
QDs and hole transport materials, this can balance the injec-
tion between electrons and holes. Therefore, key challenge
is how to exploit QDs with better matched energy level of
hole transport materials or search suitable hole transport
materials for QD layer. As a new strategy, we target to find
QD-assisted energy level that matches with hole transport
layer, and expect to improve charge injection balance in the
device, which, as a result, can simultaneously achieve high
luminescence and long lifetime.
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Here we report the design and synthesis of ideal alloyed
Zn1−xCdxSe QDs by precisely controlled shell growth. And
thus-fabricated QLED based on such Zn1−xCdxSe QDs has
achieved maximum EQE of ≈30%, maximum brightness
of over 334 000 cd m−2. It also has very low efficiency roll-
off at high current density (EQE >25% @ current density of
100 mA cm−2). With 1.9 V turn-on voltage, the operational
lifetime of QLEDs has been extended to ≈1 800 000 h at
100 cd m−2, which already fulfills the industrial requirement
for display applications. We attribute these major advances
to high quantum yield (QY) of core/shell QDs with ZnSe
as intermediate shell material, matched energy levels with
hole transport material, and suitable surface modification,
collectively resulting in balanced charge injection and high
efficiency.
2. Results and Discussion
2.1. Characterization of Quantum Dots
One of the fundamental questions guiding research is how to
obtain QY ≈100% QDs for QLED applications.[2] In our pre-
vious studies, a structure with alloyed Zn1−xCdxSe QDs and
ZnSe, ZnS shells as ideal high photoluminescent quantum
yield (PLQY) (between 40% and 75%) red emitter has been
designed and synthesized via facile “phosphine-free” wet
chemical method.[16,17] Most recently, we have further devel-
oped a “low-temperature nucleation and high-temperature shell
growth” method by which stable QDs with even higher QY
can be obtained.[18] For example, the highest PLQY of as-syn-
thesized ZnCdS/ZnS and ZnCdSe/ZnS core/shell QDs even
for blue and green emission has been boost up to ≈100%, a
significant increasement of QY over previous “high-
temperature nucleation and low-temperature shell growth”
method.[17–19] More importantly, alloyed core/shell QD ensem-
bles are thought to be able to effectively suppress the Förster
resonance energy transfer (FRET).[17] Combining with “phos-
phine-free” and “low-temperature nucleation and high-tem-
perature shell growth” together, a series of new kind of QDs
have been synthesized by adapting Zn1−xCdxSe as core, certain
thickness of ZnSe as middle shell, and ultra-thin ZnS as outer
shell, i.e., Zn1−xCdxSe/ZnSe/ZnS core/shell QDs (shown in
Figure 1a). This kind of QDs is expected to have superb charac-
teristics including single-exponential photoluminescence decay
dynamics, near-unity PLQY, and single-dot photoluminescence
nonblinking. It is also possible to have good matched energy
level in current widely used organic/inorganic hybrid device
structure, and lead to a balanced charge injection.
As for the alloyed cores, the energy levels for Zn1−xCdxSe
locate between CdSe and ZnSe.[20] The corresponding energy
band diagram of CdSe, ZnSe, and ZnS is shown in Figure 1b.
Since CdSe and ZnSe almost have the same valence band posi-
tion (difference <0.1 eV), the alloyed Zn1−xCdxSe and ZnSe
must have similar valence band and share a very small valence
band offset between them. For synthetization, the alloyed
Zn1−xCdxSe QDs, (x = 0.4) was first synthesized at 260 °C, then
it was overcoated by ZnSe and ZnS and formed ZnSe/ZnS
shell at 300 °C (Supporting Information). And the shell growth
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temperature was set to 40 °C higher than the nucleation tem-
perature. UV–vis absorption and photoluminescence spectra
of Zn1−xCdxSe, Zn1−xCdxSe/ZnSe, and Zn1−xCdxSe/ZnSe/
ZnS QDs are shown in Figure 1c. A significant PLQY boost
(from 40% to 90%) accompanied by a 4 nm blueshift (from
610 to 606 nm) is observed after the growth of ZnSe shell. It
is further shifted to 597 nm by overcoating 0.3 nm thick ZnS
shell. Both ZnSe and ZnS shells are optimized to the desired
thickness, therefore, the PLQY of corresponding QDs have
been obtained over 95%. Transmission electron microscopy
(TEM) images of core/shell QDs show excellent size disper-
sity with an average size of 15 nm (Figure 1d and Figure S1,
Supporting Information). As shown in Figure 1d, the perfect
lattice fringes without defects have been observed through
the entire particle. This indicates an excellent crystallinity
is formed during the epitaxial shell growth. We believe the
process of high temperature shell growth leads to the forma-
tion of gradient alloy shell, and therefore, it greatly reduces the
stacking faults. X-ray diffraction (XRD) pattern of Zn1−xCdxSe/
ZnSe/ZnS QDs also confirms the zinc-blende structure with
characteristic (111), (220), and (311) Bragg peaks (Figure S1,
Supporting Information).
To obtain ideal semiconductor QDs for high efficient
devices, our recent study indicates not only high PLQY
with low optical polydispersity, single-exponential PL decay
dynamics, and suppression of FRET are indispensable prop-
erties, but also the nonblinking behavior of QDs is highly
necessary.[17] Blinking generally costs photoluminescence
fluctuation between bright “on” and dark “off” states and
thus leads to low QYs.[21] By efficient passivating surface
traps and/or suppressing Auger recombination, it is possible
to realize nonblinking QDs. As shown in Figure S2 (Sup-
porting Information), total internal reflection fluorescence
microscope has been used to study single QD’s photolumi-
nescence blinking behavior. Zn1−xCdxSe/ZnSe/ZnS QDs were
diluted and immobilized into a poly (methyl methacrylate)
(PMMA) matrix, and the single-dot fluorescence traces were
recorded in a scale of 200 s. The second-order photon correla-
tion experiment has also been carried out. The average area
ratios between the central and the side peaks are all <0.5,
indicating that the measured emission light comes from a
single QD.[22,23] After the successful control of blinking, we
believe such Zn1−xCdxSe/ZnSe/ZnS core/shell QDs can be
used as an ideal red emitter to manufacture QLEDs with
improved device performance, especially targeting for high
EQE. The comparison of the performance of QLEDs based on
Zn1−xCdxSe QDs with and without ZnSe/ZnS shells has also
been confirmed in Figure S3 (Supporting Information). The
poor performance of Zn1−xCdxSe core based devices is mainly
due to the low QY (40%, Figure 1c) in solution, accompanying
by the lower QY (28%, Figure S4a, Supporting Information)
of QD films resulting from the nonradiative FRET. This pro-
cess is strongly dependent on the shell thickness of QDs. The
smaller size of Zn1−xCdxSe core QDs (≈4 nm, in Figure S4b,
Supporting Information) could make the FRET more efficient
than that of Zn1−xCdxSe/ZnSe/ZnS.[24] This is evidenced by
the comparison of the steady PL spectra between the QD
solutions and films, as shown in Figure S4c,d (Supporting
Information).
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Figure 1.  a) Schematic illustration of designed structure of Zn1−xCdxSe/ZnSe/ZnS core/shell QD. b) Energy level diagram of CdSe, ZnSe, and CdS.
c) UV–vis absorption and photoluminescence spectra of Zn1−xCdxSe/ZnSe/ZnS core/shell QDs. d) High-magnification transmission electron microscopy
image of one Zn1−xCdxSe/ZnSe/ZnS core/shell QD (Scale bar, 5 nm).

2.2. Ligand Exchange
For electroluminescent devices, the role for surface ligands is
not only to keep good solubility in solution such that it favors
better the solution-processed fabrication, but also to improve
the charge transportation among the QDs and energy transfer
between charge transport layers and QDs. Our recent studies
show the benefits of improving carrier transmission and
reducing hole injection potential barrier by using short-chain
thiol as capping ligand, such as octanethiol, tridentate thiol
etc.[19,25] Here we use 2-ethylhexane-1-thiol (EHT) as capping
ligand and its chemical structure is shown in Figure  2a.
Clearly, EHT has better solubility than octanethiol. To con-
firm the successful attachment of EHT to the core/shell QDs,
FTIR was used to compare different functional groups and
the results are shown in Figure S5 (Supporting Information).
The success of exchange can be judged from the disappearance
of stretching vibrations of carbonyl moiety in oleic acid (OA,
located at 1713 cm−1),[25] and the QDs maintain good dispersion
after ligands exchange (Figure S6, Supporting Information).
Compared to its original capping ligand OA, EHT has some
obvious advantage as follows: First, OA is easy to fall off from
the surface of QDs, and this can cause dangling bonds and sur-
face defect states, even the aggregation of QDs. It eventually
decreases the overall performance of QDs. Instead, thiol group
has a strong binding force to the surface cations of the QDs,
and is not easily detached.[19] The chelation of the thiol group
makes the combination between EHT and QDs more firmly.[25]
Second, the shorter chain of EHT helps to increase the charge
injection efficiency.[19] Finally, the most important is that
the thiol group is an electron donor group, and it can elevate
the energy level of QDs and reduce the hole injection barrier.[26]
This may increase the hole injection efficiency and improve the
charge injection balance.
To study the possible valence band shift between OA and
EHT capped QDs, ultraviolet photoelectron spectroscopy (UPS)
have been studied on these QDs (Figure 2b). It shows that the
valence band dose shift after the exchange of surface ligands
from OA to EHT. The valence band spectra were carried out
with a monochromatic He I light source (21.2 eV) and a VG
Scienta R4000 analyzer. As shown in Figure 2b, the valence band
of the QDs with OA or EHT surface ligands are calculated to be

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Figure 2.  a) Chemical structures of oleic acid (OA) and 2-ethylhexane-1-thiol (EHT). b) Ultraviolet photoelectron spectroscopy (UPS) data of Zn1−xCdxSe/
ZnSe/ZnS core/shell QDs with OA or EHT surface ligands. c) Photoluminescence decay curves of Zn1−xCdxSe/ZnSe/ZnS core/shell QDs with EHT
surface ligand in solution and solid film. d) Normalized PL spectra of Zn1−xCdxSe/ZnSe/ZnS core/shell QDs with EHT surface ligand in solution and
solid film. Insets show the PLQYs of QDs in solution and solid film.

6.48 and 6.21 eV, respectively. Since there is no photolumines-
cence peak shift in QDs with OA or EHT surface ligands, their
bandgaps are assumed to be the same, ≈2.08 eV. Therefore,
the conduction bands of these two QDs are determined to be
4.4 and 4.13 eV. The potential barrier for holes between the hole
transfer layer and QDs is reduced from 1.18 to 0.91 eV after
the surface ligand exchange from OA to EHT. In fact, the band
barrier can be reduced further as an interface dipole formed due
to the hydrogen bonding between hydroxyl group of EHT and
hole transfer layer.[26] Due to the use EHT as capping ligands,
we believe such reduction of the hole injection potential can
eventually improve the device performance.
Transient photoluminescence decay results indicate nearly
single-exponential with the lifetime of 11.4 and 14.4 ns for
QDs in solid film and in solution, respectively (Figure 2c).
The lifetime for QDs with EHT as ligands in solid film has
less change comparing to that with OA as ligands (Figure S7,
Supporting Information) and the difference between solid film
and solution is much smaller than previous reported core/
shell QDs,[27] which means that FRET has been effectively sup-
pressed. As shown in Figure 2d, there is only 2 nm peak posi-
tion shift between close-packed thin film and solution of red
Zn1−xCdxSe/ZnSe/ZnS QDs with EHT surface ligands, along
with a 2 nm increase of full width at half maximum (FWHM).
Most importantly, the PLQY of the ensemble QDs is still
kept as high as 90%. It means the surface defects have been
successfully suppressed and intrinsic radiative decay process of
red Zn1−xCdxSe/ZnSe/ZnS QDs still contributes the most. For
high EQE devices, it is crucial to keep a constant high QY after
QDs being fabricated into close-packed QD thin film from its
solution. With these superb characteristics including high QY
of emitting layer, single-exponential photoluminescence decay
dynamics, and FRET suppression, such Zn1−xCdxSe/ZnSe/ZnS
QD based QLED is highly desirable to further maximize EQE
and minimize power consumption.
2.3. Devices Fabrication
A typical multilayer structure consisting of thickness control-
lable QD layer sandwiched between an organic hole transport
layer (HTL) and an inorganic electron transport layer (ETL) has
been adapted here for constructing QLEDs (Figure  3a).[4,18,25]
The device structure is fabricated as ITO (95 nm)/PEDOT:PSS
(50 nm)/TFB (20 nm)/QDs (40 nm)/ZnO (60 nm)/Al (100 nm).
All the layers are sequentially spin-coated on glass substrates
with a pre-patterned ITO transparent anode except that Al is
deposited by thermal vacuum deposition. The diameter of
Zn1−xCdxSe/ZnSe/ZnS core/shell QDs is ≈15 nm, consist
of the radius of 2 nm Zn1−xCdxSe core, 5.3 nm ZnSe shell,
and 0.3 nm ZnS shell. This structure is confirmed by energy
dispersive spectroscopy (EDS) elemental maps of typical chem-
ical compositions of zinc, cadmium, selenium, and sulfur of
Zn1−xCdxSe/ZnSe/ZnS core/shell QDs (Figure S8, Supporting
Information). It clearly shows that the cadmium only exists in
the region corresponding to the Zn1−xCdxSe core and almost no
cadmium was observed in the ZnSe and ZnS shell. The distri-
bution of selenium is significantly larger than that of cadmium,

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Figure 3.  a) Schematic energy level diagram of multilayer QLED structure. b) Current–density versus bias for hole-only devices based on 40 nm thick
Zn1−xCdxSe/ZnSe/ZnS core/shell QDs with OA or EHT surface ligands. c) Current density and luminance versus bias for devices based on Zn1−xCdxSe/
ZnSe/ZnS core/shell QDs with OA or EHT surface ligands.
indicating that the ZnSe shell is successfully coated. It also can
be seen that the zinc distribution is larger than the selenium
distribution, indicating that the successfully growth of outer
layer is ZnS only. The sulfur distribution can be seen scattered
at very low content, indicating that the ZnS shell is very thin.
The energy dispersive EDS line scanning profiles of Cd, Zn, Se,
and S also confirmed the formation of Zn1−xCdxSe/ZnSe/ZnS
core/shell QDs (Figure S9, Supporting Information). Compared
to CdS as shell, the conduction band of ZnSe is ≈0.7 eV higher,
although its valence band is only slightly shallower (≈0.2 eV;
Figure S10, Supporting Information).[28,29] This provides much
better confinement for the electron wave function. To ensure
charge confinement in the core, it may not necessarily to have
thick ZnS shell. In particular, the reduce of the thickness of
ZnS outer shell can significantly enhance charge injection into
the device while maintaining high QD QYs. This can lead to
high efficiency and long lifetime for QLEDs.[4]
Single charge devices with only holes and electrons moving
through Zn1−xCdxSe/ZnSe/ZnS core/shell QDs with OA or
EHT as surface ligands are fabricated to study how to improve
charge and transport properties (Figure S11, Supporting Infor-
mation). From the current density versus bias characteristics of
the electron-only and hole-only devices shown in Figure 3b and
Figure S12 (Supporting Information), both the electron and
hole currents show an increase after the ligand exchange from
OA to EHT. Especially, the hole current boosts a lot with EHT
as surface ligand resulting in a well-balanced electron and hole
device structure (Figure S12b, Supporting Information). As
shown in Figure 3c, both current density and luminance exhibit
a significantly enhancement on QDs with EHT surface ligands.
For instance, the luminance of 81 000 cd m−2 is achieved at 4 V
for QDs with EHT surface ligand, over fourfold higher than
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that of QDs (17 000 cd m−2) with OA surface ligand at the same
voltage. By improving the electron and hole injection efficiency
and overall balance, it may give us an opportunity to prepare
device with ideally maximal EQE.
2.4. Devices Performance
Figure  4 presents detailed study of device performance based
on Zn1−xCdxSe/ZnSe/ZnS core/shell QDs with EHT surface
ligand. The electroluminescence spectrum is saturated with
QD emission and redshifted to 602 nm from the solution
photoluminescence at 597 nm (Figure 4a). FWHM of EL is
slightly broader from 25 to 27 nm. This 5 nm redshift in emission
position is due to the interactions between close-packed QDs.[9]
Current density and luminance performance of as-fabricated
QLED is shown in Figure 4b and related EQE results are shown
in Figure 4c,d. The brightness reaches 334 000 cd m−2, and the
EQE can reach up to 30.9% which is ≈15% higher than the
QLED with OA as ligands (Figure S13, Supporting Informa-
tion), indicating that the internal quantum efficiency is almost
100% (assuming the real maximal EQE to be over 30%) and the
electrical loss of the device is negligible. This is also confirmed
by simultaneously measuring the PLQYs and EQE on a
working LED device (Figure S14a, Supporting Information).We
noticed that PLQYs of the emitting layer in the device reduced
further when the bias was swept lower than turn-on because of
the emitting layer charge and/or electric field induced charge
separation process. Then, the PLQE starts to increase to unity
when the bias reaches the turn-on (≈1.8 V, when the device
emits light). The observation of this phenomenon is consistent
with the previous report and can be explained by the trap-filling
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Figure 4.  a) Spectra of Zn1−xCdxSe/ZnSe/ZnS core/shell QD solution photoluminescence (solid line) and QLED electroluminescence (dashed line).
b) Current density and luminance versus bias of the best-performing QLEDs based on Zn1−xCdxSe/ZnSe/ZnS core/shell QDs. c) EQE versus luminance
of the best-performing QLEDs based on Zn1−xCdxSe/ZnSe/ZnS core/shell QDs. d) EQE versus current density of the best-performing QLEDs based on
Zn1−xCdxSe/ZnSe/ZnS core/shell QDs. e) Histogram of maximum EQE measured from 30 devices. f) Stability data for a device based on Zn1−xCdxSe/
ZnSe/ZnS core/shell QDs. The device was test at ambient conditions (temperature, 20–25 °C; relative humidity, 50–70%).

effects.[30] That is, charge carriers were injected and filled in
the trap states under a suitable bias, this may eliminated trap-
mediated nonradiative recombination and resulted in enhanced
PLQE eventually. In our case, both PLQE and EQE have a cor-
relative change and they can keep the maximum value when
the device is swept from 1.8 to 3.0 V.
The device based on QDs with EHT as surface ligand also
demonstrates higher current efficiency (≈72 cd A−1) and power
efficiency (≈110 lm W−1) than the optimized device based QDs
with OA as ligands (Figure S15, Supporting Information) To the
best of our knowledge, the maximum EQE of such Zn1−xCdxSe
core/shell QDs based QLED is the highest value among all red
QLEDs (Table S1, Supporting Information). The performance
of these devices are consistent after being cross-checked and
the results are shown in Figures S16 and S17 (Supporting
Information). It is noticed that the EQE exceeded the ever
reported theoretical efficiency of ≈20% when we omitted the
additional light extraction caused by light interference.[2,5,13,31]
For multilayer panel LED, the effect of light interference is
dependent on the phase difference between two interferential
emitted light beams, and it will give an estimated correction
of 50–60% to the original extraction rate of LEDs that are not
subjected to interference effects.[31] To maximize the interfer-
ence enhancement, it is desirable to place the emission zone at
a quarter wavelength away from the reflector, which is ≈80 nm
(for emission at 600 nm and an average index of refraction of
1.8 for ZnO nanoparticles), considering that charge recombina-
tion/emission zone is in the middle of the QD layer due to the
balance injection into our device. The distance from reflector is
exactly ≈80 nm, and the final extraction rate is therefore reason-
ably improved to above 30%.
We also demonstrate the possibility of synthesis Zn1−xCdxSe/
ZnSe/ZnS QDs with different emitting colors. By selectively
choosing different ratios of the concentration of Zn to that of
Cd, QDs with photoluminescence emission peaks at 611 and
628 nm are successfully demonstrated (Figure S18a, Sup-
porting Information). As shown in Figure S18b (Supporting
Information), these red QLEDs show comparable performance
as that of the above optimized device with photoluminescence
peak at 597 nm, these devices achieve a maximum EQE of
29.5% and 28.7%, respectively, suggesting the great emitting
color tunability of these Zn1−xCdxSe/ZnSe/ZnS QDs.
Aside from the high peak EQE emphasized above, another
improved device performance is that these Zn1−xCdxSe/
ZnSe/ZnS core/shell-QD-based QLEDs can tolerate high cur-
rent densities and maintain a broad range of high efficiency
(Figure 4c,d). It also shows a very low efficiency roll-off at high
current density. EQE can be well maintained at 30% level when
the device brightness is kept between 80 and 32 000 cd m−2,
which is superior to all QLEDs reported before (Table S2, Sup-
porting Information). At the same time, when current density
is operated from 0.1 to 370 mA cm−2, EQE can be safely main-
tained above 20%. The histogram of the maximum EQE for the
30 QLEDs shows the EQE ranging from 26.5% to 30.5% with
a mean of 28.5% (Figure 4e). It has a deviation less than 10%,
suggesting excellent device reproducibility.
Stability test for a QLED device was conducted by set cur-
rent density at 20.3 mA cm−2 current corresponding to an
initial luminance of the device at 17 200 cd m−2. The device
lifetime is defined as the time for the decrease of luminance to
50% of its initial value, i.e., T50.[32] As shown in Figure 4f, the
test ran as long as 140 h. It can be converted to ≈1 800 000 h

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operation if this device is operated at 100 cd m−2 with accel-
eration factor of n = 1.84 (Figure S19, Supporting Information).
Even converted to high brightness display at 2000 cd m−2, it is
still predicted ≈7300 h. To the best of our knowledge, the opera-
tion lifetimes of those devices are comparable to those of the
previous reported best red QLEDs.[6] And again we believe that
the excellent performances of these red QLEDs are originated
to the unique QD structure as well as the stable surface modifi-
cation of the QDs. What we want to highlight here is the record
high EQE and brightness, low efficiency roll-off, excellent
reproducibility and outstanding operational stability, and the
overall performances are also comparable to the state-of-the-art
OLEDs/Ph-OLEDs produced by vacuum deposition reported
before (Tables S1 and S3, Supporting Information).
3. Conclusion
The present work demonstrates record high efficiency, low
efficiency roll-off, excellent reproducibility, and outstanding
operational stability red QLEDs. The gradient composition of
the core/shell QD with thicker ZnSe interlayer shell, ultrathin
ZnS outer shell, and high photoluminescence QY with EHT
modified surface, collectively result in balanced charge injec-
tion and high current densities. As a result, a maximum
EQE is about 30% for QLEDs with EL peak between 600 and
635 nm, which is the highest value reported based on solution-
processed devices. We believe this is a milestone and will lead
to fast development of QLED into practical display and solid-
state lighting applications, and QLED technology will widely
penetrate into our daily life in the near future.
4. Experimental Section
Synthesis of Zn1−xCdxSe/ZnSe/ZnS Core/Shell QDs:—Chemicals: All
reagents were used as received without further experimental purification.
Cadmium oxide (CdO, 99.99%), zinc oxide (ZnO, 99.9% powder),
selenium (Se, 99.99%, powder), 1-octadecene (ODE, 90%), oleic acid
(OA, 90%), 1-octanethiol (OT, 98%), and paraffin oil were purchased
from Aldrich and Adamas-beta.
Synthesis of Zn1−xCdxSe/ZnSe/ZnS Core/Shell QDs:—Preparation of
Precursors: Cadmium oleate (Cd(OA)2): CdO (20 mmol), OA (20 mL),
and ODE (30 mL) were loaded into a 100 mL three-neck flask. The
mixture was then degassed at 150 °C for 15 min. Finally, the solution
was heated to 240 °C under nitrogen to obtain a colorless clear solution.
Zinc oleate (Zn(OA)2): A mixture of ZnO (80 mmol), OA (80 mL), and
ODE (120 mL) was loaded into a 250 mL three-neck flask. The mixture
was then degassed at 150 °C for 15 min. Finally, the solution was heated
to 300 °C under nitrogen with vigorous stirring to get a colorless clear
solution. Solution of first Se precursor: It was made by degassing Se
(0.3156 g, 4 mmol), 10 mL of ODE in a 50 mL three-necked flask, then it
was sonicated for 10 min. Solution of second Se precursor: It was made
by degassing Se (1.578 g, 20 mmol), 200 mL of ODE in a 500 mL three-
necked flask, then it was heated to 220 °C until the solution turn into
transparent light yellow.
Synthesis of Zn1−xCdxSe/ZnSe/ZnS Core/Shell QDs:—Preparation of
Zn1−xCdxSe/ZnSe/ZnS QDs: The Zn1−xCdxSe cores with diameter about
≈4.5 nm were prepared using a modified literature procedure.[33] As a
typical synthetic procedure, 0.4 mmol of CdO, 1 mmol of ZnO, 15 mL
of ODE, and 2.2 mL of OA were placed in a 100 mL round flask. The
mixture was heated to 150 °C, degassed under 0.1 Torr pressure for
15 min, then it was filled with N2 gas, and further heated to 260 °C
Adv. Funct. Mater. 2019, 1808377 1808377  (7 of 9)
www.afm-journal.de
to form a clear mixture solution of Cd(OA)2 and Zn(OA)2. At this
temperature, 2 mL of the first Se precursor was swiftly injected into
the reaction flask. Successive samples were extracted to monitor their
PL spectra. The reaction temperature was kept at 260 °C for 60 min
for the core growth. For the overcoating of the ZnSe shell, a desired
amount of Zn(OA)2 and the second Se precursor (1 equivalent amount
refers to Zn(OA)2 and Se) were injected dropwise into the reaction
solution at a rate of 5 mL h−1 using a syringe pump at 300 °C. For
the consecutive overcoating of the ZnS shell, a desired amounts of
Zn(OA)2 and octanethiol (1.4 equivalent amount refers to Zn(OA)2)
were added dropwise into the reaction solution at a rate of 5 mL h−1
using a syringe pump. The thickness of the shell can be controlled
by the adding volume of the precursor. After finishing the precursor
infusion, the solution was further annealed at 300 °C for 20 min. Once
the reaction was completed, the temperature was cooled down to
room temperature. The QDs were purified using acetone or methanol.
For stability test, 10 mL of the as-synthesized core/shell QDs were
washed two times by repeated precipitation with 10 mL acetone first.
Then, the QDs were dissolved in 7.5 mL hexanes, and centrifuged
(8000 rpm, 5 min) to precipitate/remove any un-dissolved species and
by-products. QDs were purified six times by precipitation/dispersion
method with a solvent combination of hexane/ ethanol (1/1 in volume
ratio) using same centrifugation condition. Finally, the purified QDs
were redispersed into hexane or chloroform for optical characterization,
post-treatments, and the preparation of QD films.
Fabrication of Multilayered Red QLEDs: The device structure was
indium tin oxide (ITO, 95 nm), PEDOT:PSS (50 nm), TFB (20 nm), core/
shell QDs (40 nm), ZnO nanoparticles (NPs, 60 nm), and aluminum
(Al, 100 nm). ZnO NPs were synthesized by a solution-precipitation
process using Zn acetate and TMAH.[34] For a typical synthesis, a
solution of zinc acetate in DMSO (0.5 m) and 30 mL of TMAH in ethanol
(0.55 m) were mixed and stirred for 1 h in ambient air. Then ZnO NPs
were washed and dispersed in ethanol. QLEDs were fabricated on glass
substrates coated with ITO with a sheet resistance of ≈20  Ω sq−1. The
substrates were cleaned with deionized water, acetone, and isopropanol,
consecutively for 15 min each. These substrates were spin-coated with
PEDOT:PSS (AI 4083) and baked at 150 °C for 15 min in air. The coated
substrates were transferred to a N2-filled glove box for spin-coating of
TFB, QDs, and ZnO NPs. As hole transport layer, TFB were spin-coated
using 1.5 wt% in chlorobenzene (2000 rpm for 30 s), followed by baking
at 110 °C for 30 min. Then, it was spin-coated by QDs (15 mg mL−1, in
toluene) and ZnO NPs (30 mg mL−1, in ethanol), followed by baking at
145 °C for 30 min. The spin speed was 1000 rpm for the QD layer and
3000 rpm for the ZnO layer to achieve layer thickness of ≈20 and ≈30 nm,
respectively. These multilayer structure samples were then loaded into
a custom high-vacuum deposition chamber (background pressure,
≈3 × 10−7 torr) to deposit the top Al cathode (100 nm thick) patterned by
an in situ shadow mask to form an active device area of 4 mm2.
PL Intensity Trace Measurement for Single QD: To collect the PL
intensity of a single QD, the concentration of QD solution was very
low. First, the purified QD solution was diluted by PMMA solution
(PMMA: toluene = 5 wt%, magnetic stirring at 45 °C for 24 h). Then,
the diluted QD solution was spun cast onto a fused silica substrate at
5000 rpm for 20 s. 405 nm output of a 5 MHz picosecond diode laser
or 400 nm output of a CW laser was used as the excitation source. The
laser beam was focused onto the sample substrate by an immersion-oil
objective (NA = 1.4). The PL signal of a single QD was collected by
the same objective and sent through a 0.5 m spectrometer to a charge
coupled-device camera for PL spectral measurement. The PL signal of a
single QD can be alternatively sent through an on polarizing 50/50 beam
splitter to two avalanche photodiodes (APDs) in a time-correlated single
photon counting (TCSPC) system with a time resolution of ≈250 ps.
The TCSPC system was operated under the time-tagged, time-resolved
mode so that the arrival times of each photon relative to the laboratory
time and the laser pulse time could both be obtained, which allowed to
plot the PL time trajectory. Moreover, the delay times between photons
collected by one APD and those by the other could be summed up to
yield the second-order auto correlation g2(τ) functions.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Calculations of the EQE: The EQE is calculated according to the
formula below[35,36]
ηEQE =
π Le ∫ I ( λ ) λ dλ (1)
K mhcJ I ( λ )V ( λ ) dλ
∫ Received: November 24, 2018
where e is the electron charge, h is the Planck’s constant, c is the
velocity of light, and Km  = 683 lm W−1 is the maximum luminous
efficacy.[35,36] The current density J is measured from the current
density–voltage characteristics using an Agilent 4155C semiconductor
parameter analyzer with a calibrated Newport silicon diode under
ambient conditions. I(λ) is the relative electroluminescence intensity at
wavelength λ, obtained from the EL spectrum measured with an Ocean
Optics spectrometer (USB2000, relative irradiance mode) supplied
by a Keithley 2400 source meter, and V(λ) is the normalized photonic
spectral response function. L is the total luminance, which is calibrated
using a Minolta luminance meter (LS-100).
Characterization: UV–vis absorption and PL spectra were measured by
Ocean Optics spectrophotometer (model PC2000-ISA). All the QYs data
of QDs were collected through Ocean Optics USB2000 spectrometer
and an Ocean Optics ISP-50-8-I integrating sphere. The solid-state
QD films were prepared by spin-coating the purified QD solution at
1000 rpm for 30 s on pre-cleaned glass substrates (size: 2.0 × 2.0 cm2).
Then, the PLQY of these QD thin-films were measured in an integrating
sphere by an absolute PL QY measurement system (Ocean Optics
ISP-50-8-I). Time resolved fluorescence spectra were measured via the
time-correlated single-photon counting method using a JY HORIBA
FluoroLog-3 fluorescence spectrometer with a 405 nm ps pulsed diode
laser at 1 MHz repetition rate and ≈200 ps pulse duration. The optical
density (OD) values of the QD samples at the excitation wavelength
were all in the range of 0.02–0.05. Transmission electron microscopy
studies were performed using a JEOL JEM-2010 electron microscope
operating at 200 kV. Aberration corrected high-angle annular dark field
scanning transmission electron microscopy (HAADF-STEM) images
were obtained on JEOL ARM200F operated at 200 kV. The energy
dispersive spectroscopy mappings were carried out by four symmetrical
designed EDS detectors equipped on FEI Talos F200X. The cross-section
images of the QLEDs were carried out using FEI Talos F200X TEM. The
phase and the crystallographic structure of the QDs were investigated
by X-ray diffraction (D8-ADVANCE). Current density–voltage (J–V)
characteristics of QLEDs were conducted using an Agilent 4155C
semiconductor parameter analyzer with a calibrated Newport silicon
diode under ambient conditions. The luminance was calibrated using
a Minolta luminance meter (LS-100). The electroluminescence spectra
were obtained with an Ocean Optics spectrometer (USB2000, relative
irradiance mode) and a Keithley 2400 source meter.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
J.S. and O.W. contributed equally to this work. The authors gratefully
acknowledge the financial support from the National Natural Science
Foundation of China (Grant Nos. 61874039, 21671058, and 51802079)
and the Open Project of Key Laboratory of UV-Emitting Materials
and Technology of Ministry of Education (Grant No: 130028854).
The authors thank Prof. Aiwei Tang of Beijing Jiaotong University and
Prof. Lei Wang of Huazhong University of Science and Technology for
cross-checking the LED measurement system.
Conflict of Interest
The authors declare no conflict of interest.
Adv. Funct. Mater. 2019, 1808377 1808377  (8 of 9)
www.afm-journal.de
Keywords
charge balance, efficiency, light-emitting diodes, quantum dots, surface
ligands
Revised: April 29, 2019
Published online:
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