QD-LEDs fabricated based on low toxicity QDs also showed
some progress. The maximum brightness utilizing I–III–VI
semiconductor QDs have reported over 1000 cd m
−2
in the
yellow-red area without the demonstration of external
quantum efficiency (EQE).
21,32
For those using the III–V heavy-
metal-free QDs, such as InP/ZnSeS QDs, the maximum EQE
can reach more than 3% with an electroluminescence (EL)
peak at 518 nm and show a full width at half-maximum
(FWHM) of about 64 nm.
33
These results demonstrate good
color tunability and competitive efficiencies for heavy-metal-
free QD-LEDs in the range of 510 to 630 nm, but still lack good
results on the violet-blue emission QD-LEDs due to the
absence of corresponding heavy-metal-free QD emitters. There-
fore, one of the main challenges is the development of
efficient violet-blue emitters and the realization of higher
efficiency QD-based LEDs using heavy-metal-free QDs.
So far, for the heavy-metal-free QDs, no matter I–III–VI or
III–V QDs, all cannot obtain high QYs (>70%) and high stabi-
lity QDs in the violet-blue area, let alone high brightness and
efficiency of corresponding violet-blue QD-LEDs. Most recent
studies have begun to concentrate on the synthesis of wide
bandgap ZnSe QDs as potential violet-blue emitter. Our pre-
vious report showed an impressively high QY of 70%,
30
but the
stability of ZnSe related QDs is still unsatisfied. Previously
reported red-green and Cd-containing blue QD emitters
showed QYs of up to 90% with high stabilities,
14–16
and these
results all indicate the immediacy of the QY and stability
improvement of violet-blue ZnSe QDs. Therefore, the synthesis
of violet-blue QDs that can simultaneously satisfy high PL QYs
(>80%), narrow and symmetric emission (FWHM < 20 nm),
high stability, environmentally friendliness, and low cost is an
urgent requirement for the realization of heavy-metal-free
violet-blue and thus full-color QD-LEDs. Herein, we present a
method for the synthesis of violet-blue emitting ZnSe/ZnS
core/shell QDs that show high QYs as well as high stability.
Different from most of the traditional nucleation at high temp-
erature/shell growth at low temperature methods, we adopt a
lower temperature injection and higher temperature growth
method for the synthesis of ZnSe/ZnS core/shell QDs.
14–16
Nearly monodisperse ZnSe/ZnS core/shell QDs were syn-
thesized with high absolute PL QYs (up to 80%), high color
purity (with an FWHM of about 12–20 nm), and good color
tunability in the violet-blue range from 400 to 455 nm.
Importantly, such ZnSe/ZnS core/shell QDs showed very good
chemical/photochemical stability compared with previous
studies.
27,30
Furthermore, violet QD-LEDs using ZnSe/ZnS core/shell
QDs have also been successfully demonstrated with a fully
solution-processed method. Highly bright violet QD-LEDs
show a maximum luminance of 2632 cd m
−2
and a peak EQE
of 7.83%. In a sense, such brightness and efficiency exhibit
huge superiority to those of the best Cd-based violet-blue
QD-LEDs considering the factors of the photopic luminosity
function. These results may offer a practicable platform for the
realization of heavy-metal-free QD based violet-blue and full-
color displays and lighting.
Experimental section
Chemicals
All reagents were used as received without further experi-
mental purification. Zinc oxide (ZnO, 99.99% powder), sulfur
(S, 99.98%, powder), 1-octadecene (ODE, 90%), oleic acid (OA,
90%), octanethiol (OT, 98%), zinc acetate (99.99%), dimethyl
sulphoxide (DMSO, 99.7%), tetramethylammonium hydroxide
(TMAH, 97%), and selenium (Se, 99.99%, powder) were pur-
chased from Aldrich. Chlorobenzene (analytical grade),
hexanes (analytical grade), paraffin oil (analytical grade), and
methanol (analytical grade) were obtained from Beijing Chemi-
cal Reagent Ltd, China.
Typical synthesis of ZnSe/ZnS with low temperature
nucleation/high temperature shell growth method
Stock solution for the Zn precursor: A mixture (20 mL in total) of
ZnO (0.488 g, 6 mmol), oleic acid (18 mmol, 5.076 g), and
14 mL paraffin oil was loaded in a 100 mL three-necked flask
and heated to 300 °C under nitrogen to obtain a clear solution.
Zn precursor solution was stored at 120 °C for subsequent use.
Stock solution for the Se precursor: Se (0.237 g, 3 mmol) and
30 mL of ODE were mixed in a 100 mL three-necked flask.
Under nitrogen flow and stirring, the mixture was heated to
220 °C for 180 min, and then the reaction solution was cooled
down to room temperature. Se precursor solution was stored at
50 °C for subsequent use. Synthesis of ZnSe QDs with lower
temperature and synthesis of ZnSe/ZnS core/shell QDs with high
temperature: octanethiol as the S precursor and ligands for the
synthesis of ZnSe/ZnS core/shell QDs: The ZnSe core was pre-
pared according to the previous literature of our group (see
ESI†).
30
In a typical synthesis, 2 mL Se precursor and 8 mL
paraffin oil were heated to 300 °C under nitrogen flow in a
100 mL flask. Next, 1.3 mL Zn precursor solution was injected
and maintained for 5 min for the formation of ZnSe core QDs
(Fig. S1† and Fig. 1a). Subsequently, the reaction temperature
was set at 320 °C without any purification steps, and then
2 mL OT mixed with 20 mL of Zn precursor was added at a rate
of 6 mL h
−1
. All the shell growth processes lasted for 4 h.
Aliquots of QDs were taken during the reaction to analyze the
development of ZnSe/ZnS core/shell QDs (Fig. 1). After the
reaction was completed, the temperature was cooled down
to room temperature and the QDs were purified using acetone
or methanol. ZnSe/ZnS core/shell QDs with different
shell growth temperatures (as shown in Fig. 3) were prepared
following the same procedures as that described above for the
synthesis of ZnSe/ZnS core/shell QDs at 320 °C, with a range
of different growth temperatures of 240 °C, 260 °C, 280 °C,
300 °C, and 340 °C, respectively (see ESI †). S-ODE as the
S precursor for the synthesis of ZnSe/ZnS core/shell QDs: the syn-
thesis of ZnSe/ZnS core/shell QDs with S-ODE as the S pre-
cursor was similar to the aforementioned method, except that
octanethiol was replaced by conventional S-ODE (0.2 M) as the
S precursor.
Paper Nanoscale
2952
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