pubs.acs.

org/JPCL Letter

Near-Unity Photoluminescence Quantum Yield and Highly

Suppressed Blinking in a Toxic-Metal-Free Quantum Dot
Swarnali Ghosh, Saptarshi Mandal, Soumen Mukherjee, Chayan K. De, Tridib Samanta, Mrinal Mandal,
Debjit Roy, and Prasun K. Mandal*
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ABSTRACT: There is no literature report of simultaneously achieving near-unity PLQY

(ensemble level) and highly suppressed blinking (ultrasensitive single-particle spectroscopy
(SPS) level) in a toxic-metal-free QD. In this Letter we report accomplishing near-unity PLQY
(96%) and highly suppressed blinking (>80% ON fraction) in a toxic-metal-free CuInS2/
ZnSeS Core/Alloy-Shell (CAS) QD. In addition, (i) gigantic enhancement of PLQY (from
15% (Core) to 96% (CAS QD)), (ii) ultrahigh stability over 1 year without significant
reduction of PLQY at the ensemble level, (iii) high magnitude (nearly 3 times) of electron
detrapping/trapping rate, and (iv) very long ON duration (∼2 min) without blinking at the
SPS level enable this ultrasmall (∼3.3 nm) CAS QD to be quite suitable for single-particle
tracking/bioimaging. A model explaining all these excellent optical properties has been
provided. This ultrabright CAS QD has been successfully utilized toward fabrication of low-
cost microcontroller-based stable and bright yellow and white QD-LEDs.

A chieving near-unity photoluminescence quantum yield

(PLQY) and highly suppressed blinking in a small-sized
(<10 nm) and visible light emitting quantum dot (QD) has
highly reproducible method with easily available chemicals has
been briefly outlined in Scheme 1. CuI, In(Ac)3, and DDT

been an ominous challenge, and reaching that pinnacle in a Scheme 1. Synthesis of CuInS2 Core and CuInS2/ZnSeS
non-toxic-metal-based, extremely stable QD makes it a near- CAS QDs
impossible task. Near-unity PLQY has so far been achieved in a
few nanomaterials or QDs containing toxic metals such as Cd/
Pb.1−6 However, serious concerns about sustainability of toxic-
metal-based QDs have been raised.7−9 Moreover, toxic-metal-
based QDs are not so stable, e.g., for 1 year, under ambient
conditions.1,4−6 Additionally, significant blinking with short
ON times jeopardizes the applicability of these toxic-metal-
based QDs. Hence, strong quest for achieving all these unique
properties in a toxic-metal-free QD is very active.
As a choice of toxic-metal-free QD we opted for the
relatively less explored CuInS2 QD. However, the same is very
weakly photoluminescent (PLQY ∼ 10%) because of exciton
trapping by surface defects.10−12 Even with CuInS2/ZnS or were taken into a three-neck round bottomed flask and
CuInS2/ZnSe Core/Shell QDs, near-unity PLQY could not be degassed under a vacuum at 80 °C for 1 h until a clear solution
achieved.10,13−17 However, if near-unity PLQY can be achieved was obtained (Scheme 1). The temperature of the solution was
in any toxic-metal-free QD, then the same holds the promise to then raised to 210 °C under a N2 atmosphere and heated for
replace toxic-metal-based QDs for several applications such as different durations for different extents of Core growth. For
ZnSeS Alloy-Shell growth, a mixture of Zn(St)2, OA, and ODE
LEDs or solar cells.18−20 In this Letter, we have explored a
novel strategy of alloy-shelling, i.e., ZnSeS alloy-shelling over
Core CuInS2 QD (Figure S1 and Table S1). We report Received: November 27, 2020
achieving near-unity PLQY, highly suppressed blinking in Accepted: January 25, 2021
highly stable (more than 1 year), small-sized (size <5 nm), and
toxic-metal-free CuInS2/ZnSeS QDs. The CuInS2 Core QD
has been synthesized via an inert atmosphere hot injection
method with some modifications of a reported protocol.10 This

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jpclett.0c03519

1426 J. Phys. Chem. Lett. 2021, 12, 1426−1431
The Journal of Physical Chemistry Letters
was preheated at 200 °C for 1 h until a clear solution formed.
Then, this preheated mixture along with S-TOP solution and
Se-TOP solution were injected simultaneously and dropwise to
the previously formed CuInS2 Core solution for over 20 min.
The reaction mixture was then heated at 200 °C for 2 h for
further Shell growth (Scheme 1). Detailed syntheses and
purification steps have been described in the Supporting
Information (section Ib).
Steady-State Photophysics. The absorption and emission
spectra of Core CuInS2 QD and CuInS2/ZnSeS CAS QD
have been depicted in Figure 1a (also see Figure S2 and Table
Figure 1. Absorption and emission spectra of CuInS2-based Core and
CAS QD (a) (plots normalized at the band edge), gigantic
enhancement of PLQY from Core (15%) to CAS QD (96%) (λex =
500 nm) (b), photostability comparison of different types of QDs (c),
and constancy of PLQY of the CuInS2/ZnSeS CAS QD in ambient
atmosphere for 1 year (d).
S2). A large magnitude Stokes shift of ∼150 nm and a
maximum PLQY of 15% have been obtained for Core CuInS2
QD (Figure 1b). These values are consistent with literature
data.10,11,20 A blue shift of 62 nm for the PL emission
maximum and more importantly a gigantic amplification of
PLQY from 15% to 96% have been observed because of alloy-
shelling (Figure 1b). Thus, we could achieve the first
extraordinary feat of near-unity PLQY for a toxic-metal-free
CuInS2/ZnSeS CAS QD.
It has been observed that the CuInS2/ZnSeS CAS QD is
much more photostable than CuInS2-based Core and the
photostability of the CuInS2/ZnSeS CAS QD is comparable to
the best robust QDs (but with a toxic metal), i.e., CdSe-based
CAS QD, retaining ∼90% of PL intensity after 24 h continuous
UV (365 nm) irradiation (Figure 1c). It is well-known that the
other toxic-metal-based QDs with near-unity PLQY suffer from
severe stability issues under an ambient atmosphere and are in
general not stable for 1 year.1,4−6 However, PLQY of CuInS2/
ZnSeS CAS QD, kept under normal ambient conditions, does
not decrease significantly over 1 year (Figure 1d), signifying
remarkable physical stability of CuInS2/ZnSeS CAS QD. Thus,
at the ensemble level, CuInS2/ZnSeS CAS QD exhibited
excellent optical properties and remarkable physical stability.
Time-resolved optical behavior of CuInS2-based Core and
CAS QDs have been investigated thoroughly (Figure S3 and
Table S3) and they have been structurally characterized
(Figures S5−S7 and Tables S4 and S5). It is important to
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pubs.acs.org/JPCL Letter
mention here that the size of the CAS QD is quite small (<3.3
nm, Figure S5).
Highly Suppressed Blinking Behavior: Ultrasensitive Single-
Particle Spectroscopic Exploration. In order to establish optical
superiority, a QD should exhibit excellent optical behavior at
both the ensemble and single-particle levels. Although many
QDs exhibit excellent optical properties at the ensemble level,
they exhibit severe blinking and bleaching at the single-particle
level. Single-particle spectroscopic (SPS, see SI section IX)
time traces (Figure 2a) and the corresponding well-separated
Figure 2. SPS time trace (a), bimodal intensity distribution (b),
distribution of ON fraction (c) and OFF fraction (d), probability
density distribution of ON event durations (e), and OFF event
durations (f) of CuInS2/ZnSeS CAS QD. λex = 514 nm.
bimodal PL intensity distributions (Figure 2b) clearly depict
well-resolved ON and OFF states. Intensity values above the
dashed line are considered to be ON and below the line are
considered to be OFF. As can be seen from Figure 2a,b, this
CuInS2/ZnSeS CAS QD mostly remains in the ON state,
exhibiting very minimal blinking.
The peak of the ON-fraction distribution (Figure 2c and
Table 1) was at 0.81 for CuInS2/ZnSeS CAS QD. Such a high
value indicates that highly suppressed blinking is achieved in
this CAS QD.
OFF fraction distribution, shown in Figure 2d, has a peak at
0.19. The probability density distribution of ON and OFF
event durations (Figure 2e,f, respectively) were fitted well with
the truncated power law with an additional exponential
(TPLE) equation (see SI section IX for details). The smaller
magnitude of mON (1.42) in comparison to mOFF (1.99) (Table
1) signifies ON events are much more probable than OFF
events in our CuInS2/ZnSeS CAS QD. Truncation (Figure
2e,f) at longer event durations for both ON and OFF events
indicates that an additional rate process with a single rate
constant is involved within the blinking framework.21−28 The
ON (or OFF) event truncation time is a signature of the
trapping (or detrapping) process.
https://dx.doi.org/10.1021/acs.jpclett.0c03519
J. Phys. Chem. Lett. 2021, 12, 1426−1431
The Journal of Physical Chemistry Letters pubs.acs.org/JPCL Letter

Table 1. Optical Spectroscopic Parameters Related to Ensemble and Single-Particle Spectroscopy

For CuInS2/ZnSeS CAS QD, the ON truncation time is

quite long (∼71.4 s) in comparison to OFF truncation time
(∼25.0 s) (Figure 2e,f and Table 1), indicating the high (∼3
times) value of the electron detrapping/trapping rate, which
signifies electrons stay for smaller times in trap states, and thus
higher extents of longer ON times in comparison to OFF times
is observed. Quite interestingly, extended ON duration (nearly
2 min) without blinking has been observed. Comparatively
much smaller values of mON with respect to mOFF and higher
values of the electron detrapping/trapping rate (Table 1)
signify excellent properties of the CAS QD.
In the literature, an additional exponential component in the
TPLE equation has been attributed to photoinduced hole
trapping for ON events and hole detrapping for OFF
events.22−25 If the hole gets trapped after electron trapping,
subsequent excitations would result in only radiative
recombination of the electron and hole; i.e., a quite long ON
event would be observed, without blinking. A nearly 3 times
longer hole trapping time with respect to hole detrapping time
(i.e., τD,ON/τD,OFF, Table 1) is the reason behind very long ON
events (nearly 2 min) without blinking. Such an observation
enables this toxic-metal-free QD to be quite suitable for single-
particle tracking in the biological medium. Such experiments
are currently underway. Figure 3. Energy diagram with more trap states in CuInS2-based Core
We now compare our results with serious and so far the best (a), much less traps in CAS QD with a higher extent of detrapping
results reported in literature for visible color emitting CuInS2- than trapping leading to near-unity PLQY and highly suppressed
based toxic-metal-free QDs.29 For a comparatively large-sized blinking (b), and significant hole trapping leading to extended ON
CuInS2/ZnS thick-shell QD with an apex to apex distance of state without blinking in CAS QD (c).
12.5 nm (ours is 3.3 nm), PLQY is reported to be 50% (ours is
96%) at the ensemble level. At the SPS level <ON fraction> shelling. In CAS QD, the crystalline parameters do not change
has been reported to be only 63% (ours is >80%), and with an abruptly, rather they change smoothly and gradually, thereby
mON value of 1.5 (ours is 1.42) and mOFF value of 1.65 (ours is minimizing trap states very significantly (Figure 3b). Thus,
1.99). Thus, with our CuInS2-based CAS QD of nearly 4 times near-unity PLQY (96%) and highly suppressed blinking (peak
smaller size, we could achieve much improved excellent optical of ON fraction = 81%) are achieved in our CuInS2/ZnSeS
properties in comparison with the best literature reports at CAS QD. In our CAS QD, the magnitude of Stokes shift has
both the ensemble and SPS levels. been reduced very significantly from that observed in the
It is now pertinent to explain the much improved optical CuInS2 Core QD (80 nm in comparison to 150 nm). This
properties of our CuInS2/ZnSeS CAS QD at both the observation indicates near-complete removal of deep trap
ensemble and SPS levels with the help of an energy diagram states in the CAS QD system. However, the existence of a
(Figure 3). In CuInS2 Core QD there remains (a) a very shallow trap state mediated PL emission cannot be ruled out.
significant extent of defect states that are quite effective in In that scenario it can be concluded that the nature of deep
trapping the electrons. (b) The Bohr exciton radius for CuInS2 traps and shallow traps are quite different. More work needs to
Core QD (4.1 nm)30 is larger than its size (∼2.5 nm). These be carried out to understand the origin of such an interesting
facts lead to the enhanced extent of nonradiative decay phenomenon. In our CAS QD system we have obtained highly
pathways, thereby reducing PLQY (to 15%) very significantly extended ON time (nearly 2 min) without blinking. This is a
(Figure 3a). Moreover deep-trap-assisted PL emission causes a very interesting observation because in most of the QDs this
significant Stokes shift (∼150 nm) in Core QD (Figure magnitude is very small which jeopardizes single-particle
3a).10,11,20 tracking in a biological medium. Observation of a nearly 2
These detrimental effects could be nearly circumvented by min ON state without blinking and without reduction of any
creating a potential energy barrier to stop the escape of the intensity can be explained invoking hole trapping. After
exciton, as well as maintaining minimal change in the electron trapping, if the hole gets trapped, then subsequent
crystalline behavior of the Core and Shell through alloy- excitations will lead to only radiative recombination of an
1428 https://dx.doi.org/10.1021/acs.jpclett.0c03519
J. Phys. Chem. Lett. 2021, 12, 1426−1431
The Journal of Physical Chemistry Letters
exciton (Figure 3c). Thus, we could explain all the excellent
optical properties of CuInS2/ZnSeS CAS QD obtained at both
the ensemble and SPS levels.
Application toward Low-Cost Yellow and White LED
Fabrication. Outstanding optical qualities of CuInS2/ZnSeS
CAS QD have been explored toward successful fabrication of
bright yellow LED (Figure 4). Non-toxic QDs or nanomateri-
Figure 4. Microcontroller-based low-cost LED fabrication (a) (circuit
diagram, inset of a), images of fabricated bright yellow (b) and white
LEDs (c), CIE color coordinates (d, e), and stability of LED emission
under continuous illumination (f, g) for fabricated yellow and white
LEDs, respectively.
als with near-unity PLQY are of significant potential interest
for several applications in LEDs or the bioimaging field.31−35
Instead of going for state-of-the-art but costly LED
fabrication,36−42 we have adopted low-cost “Arduino Uno”
(microcontroller board, an open-source electronics platform
based on easy-to-use hardware and software, (see https://
www.arduino.cc/)) based fabrication of LEDs (for details of
fabrication, see SI section X). This microcontroller board was
connected to a computer with a USB cable or a simple battery
to get started (Figure 4a). In principle, with this low-cost
technique, any visible color LED can be fabricated. We have
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pubs.acs.org/JPCL Letter
fabricated bright yellow and white LEDs (Figure 4b,c). CIE
coordinates of (0.48, 0.50) (Figure 4d) indicate a near-pure
yellow color, and (0.32, 0.33) coordinates (Figure 4e) indicate
bright natural white light emission. These bright yellow as well
as white QD-LEDs are quite stable, exhibiting negligible
reduction of intensity over 12 h of continuous illumination
(Figure 4f,g for yellow and white lights, respectively). Thus,
not only did CuInS2/ZnSeS CAS QD exhibit excellent
properties at both the ensemble and SPS levels but also the
same could be explored successfully toward fabricating low-
cost and highly stable QD-LEDs.
All the above-mentioned results, i.e., (a) near-unity PLQY
(96%), (b) >80% ON fraction, (c) smaller mON magnitude in
comparison to mOFF, (d) ∼3 times longer electron detrapping/
trapping rate, (e) ∼3 times higher magnitude of hole
detrapping rate/trapping rate (i.e., τD,ON/τD,OFF), and (f)
extended ON duration (∼110 s) without blinking, in a (g)
non-toxic-metal based, (h) small-sized, and (i) ultrastable (>1
year) CuInS2/ZnSeS CAS QD signifies optical supremacy of
the same over any other toxic-metal-free QD reported so far in
literature.
However, there is one drawback in this QD. A large FWHM
(∼110 nm) of the PL emission spectrum needs to be reduced
significantly. Efforts in this direction are currently underway.
In conclusion, we have achieved near-unity PLQY (96%)
and highly suppressed blinking (>80% ON fraction) in toxic-
metal-free, ultrasmall (∼3.3 nm), and highly stable (over a year
without significant reduction of PLQY) CuInS2/ZnSeS CAS
QD. Additionally, a nearly 3 times higher relative ratio of
electron detrapping rate with respect to the trapping rate has
been noted. Moreover, very long ON duration (nearly 2 min)
without blinking enables this QD to be quite suitable for
single-particle tracking in biological medium. All these
properties signify optical supremacy of this CAS QD over
any toxic-metal-free QD reported so far in literature. This
ultrabright CAS QD could be successfully employed toward
microcontroller-based low-cost fabrication of bright and stable
yellow and white emitting QD-LEDs.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpclett.0c03519.
Single-particle blinking video for CAS QD (MP4)
Synthesis of CuInS2-based QDs, structural character-
ization (TEM, EDS, and PXRD analysis), band
positions, absorption and emission spectra, PLQY
measurement, PL traces, time constants, optical
parameters, d-spacing values, experimental details for
ensemble and single-particle experiments, probability
density distributions, LED applications and images, and
comparison of literature data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Prasun K. Mandal − Department of Chemical Sciences and
Centre for Advanced Functional Materials, Indian Institute of
Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0002-5543-5090; Email: prasunchem@iiserkol.ac.in
https://dx.doi.org/10.1021/acs.jpclett.0c03519
J. Phys. Chem. Lett. 2021, 12, 1426−1431
The Journal of Physical Chemistry Letters
Authors
Swarnali Ghosh − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0003-1029-165X
Saptarshi Mandal − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0003-2837-9895
Soumen Mukherjee − Department of Chemical Sciences,
Indian Institute of Science Education and Research (IISER)
Kolkata, Mohanpur, West Bengal 741246, India;
orcid.org/0000-0002-6428-7878
Chayan K. De − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0003-4370-9004
Tridib Samanta − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0002-2079-8553
Mrinal Mandal − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0002-3596-7970
Debjit Roy − Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Kolkata,
Mohanpur, West Bengal 741246, India; orcid.org/0000-
0001-5615-3709
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.0c03519
Author Contributions
P.K.M. envisaged the project. P.K.M., D.R., and S. Mandal
established the home-built single-particle spectroscopic setup.
S.G. and T.S. synthesized and characterized the QD. S.G. and
S. Mandal recorded and analyzed ensemble level optical
spectroscopic data. S.G. and S. Mukherjee performed single-
particle level measurements, and S.G. and C.K.D. analyzed the
data. S.G. and M.M. performed white light generation
experiments. S.G. and P.K.M. wrote the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
P.K.M. thanks IISER Kolkata for financial help and
instrumental facilities. Support from the SERB-DST India,
Project No. CRG/2019/003605, is gratefully acknowledged.
S.G., S. Mukherjee, and C.K.D. thank DST-INSPIRE, S.
Mandal thanks IISER Kolkata, M.M. and D.R. thank CSIR, and
T.S. thanks the above-mentioned SERB project, for their
respective fellowship.
■
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