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Citation Yassitepe, E., Yang, Z., Voznyy, O., Kim, Y., Walters, G., Castañeda, J.
(published version) A., Kanjanaboos, P., Yuan, M., Gong, X., Fan, F., Pan, J., Hoogland, S.,
Comin, R., Bakr, O. M., Padilha, L. A., Nogueira, A. F. and Sargent, E.
H. (2016), Amine-Free Synthesis of Cesium Lead Halide Perovskite
Quantum Dots for Efficient Light-Emitting Diodes. Adv. Funct.
Mater.. doi:10.1002/adfm.201604580
Publisher’s Statement This is the peer reviewed version of the following article: Yassitepe, E.,
Yang, Z., Voznyy, O., Kim, Y., Walters, G., Castañeda, J. A.,
Kanjanaboos, P., Yuan, M., Gong, X., Fan, F., Pan, J., Hoogland, S.,
Comin, R., Bakr, O. M., Padilha, L. A., Nogueira, A. F. and Sargent, E.
H. (2016), Amine-Free Synthesis of Cesium Lead Halide Perovskite
Quantum Dots for Efficient Light-Emitting Diodes. Adv. Funct.
Mater.. doi:10.1002/adfm.201604580, which has been published in final
form at https://dx.doi.org/10.1002/adfm.201604580. This article may
be used for non-commercial purposes in accordance with Wiley Terms
and Conditions for Self-Archiving.
Always cite the published version, so the author(s) will receive recognition through services that track
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DOI: 10.1002/ ((please add manuscript number))
Amine-free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient
Light-Emitting Diodes
Emre Yassitepe,, Zhenyu Yang, Oleksandr Voznyy, Younghoon Kim, Grant Walters, Juan
Andres Castañeda, Pongsakorn Kanjanaboos, Mingjian Yuan, Xiwen Gong, Fengjia Fan, Jun
Pan, Sjoerd Hoogland, Riccardo Comin, Osman Bakr, Lazaro A. Padilha, Ana F. Nogueira,
Edward H. Sargent*
Dr. Emre Yassitepe, Dr. Zhenyu Yang, Dr. Oleksandr Voznyy, Dr. Younghoon Kim, Grant
Walters, Dr. Pongsakorn Kanjanaboos, Dr. Mingjian Yuan, Xiwen Gong, Dr. Fengjia Fan, Dr.
Sjoerd Hoogland, Dr. Riccardo Comin, Prof. Dr. Edward H. Sargent
Instituto de Química, Universidade Estadual de Campinas, Caixa Postal: 6154, CEP: 13083-
970, Campinas, São Paulo, Brazil
Instituto de Fisica “Gleb Wataghin”, UNICAMP, P.O. Box 6165, 13083-859 Campinas, Sao
Paulo, Brazil
Solar and Photovoltaic Engineering Research Center (SPERC), King Abdullah University of
Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia
1
Abstract
Cesium lead halide perovskite quantum dots (PQDs) have attracted significant interest
for optoelectronic applications in view of their high brightness and narrow emission
purification from the synthesis solution. This is attributed to proton transfer between oleic
acid and oleylamine surface capping agents that leads to facile ligand loss. Here we report
a new synthetic method that enhances the colloidal stability of PQDs by capping them
solely using oleic acid (OA). We use quaternary alkylammonium halides as precursors,
eliminating the need for oleylamine. This strategy enhances the colloidal stability of OA
capped PQDs during purification, allowing us to remove excess organic content in thin
films. We fabricate inverted red, green and blue PQD light-emitting diodes (LED) first
robustness of OA capped PQDs to solution processing. The blue and green LEDs exhibit
improved performance in EQE being threefold for green and tenfold for the blue LEDs
also report the brightest blue LED based on all inorganic CsPb(Br1-xClx)3 PQDs.
1. Introduction
Solution-processed hybrid and inorganic lead halide perovskites are of interest for
perovskites are top contenders in solution-processed single junction solar cells, having recently
passed the 22% certified power conversion efficiency milestone.[1,3] Organic Lead Halide
2
perovskites are also explored in photodetectors,[4–6] lasing applications,[7,8] and light-emitting
diodes (LEDs).[9–11]
Rapid advances in bulk perovskite materials have in turn brought significant attention
to quantum dots based on perovskites. Colloidal organic metal halide perovskite nanomaterials
hot injection synthesis method was then developed to generate fully inorganic CsPbX3
perovskite quantum dots (PQDs)[13] that showed narrow photoluminescence (PL) spectra and
high photoluminescence quantum yields (PLQY) that reached 90%. Furthermore, MAPbX3
PQDs were reported with PLQY of 70% and a wide color gamut.[14] CsPbX3 PQDs have
To date, colloidal perovskite nanocrystal syntheses have adopted lead halides as the
source for lead and halogens, a strategy similar to that used to prepare bulk perovskites
materials. This requires dissolution of PbX2 salts in a polar medium such as dimethylformamide
(DMF), and it also demands the use of a mixture of oleylamine and OA as surfactants.[12,14–16]
A non-polar solvent method was reported for CsPbX3 PQDs in which PbX2 salts were
However, these PQDs exhibited poor colloidal stability and readily precipitated from the crude
solution.[13,18,19] Recently, Hens, Kovalenko and co-workers explained the reasons for the
limited stability of PQDs, attributing it to facile proton exchange between the oleate and amine
surfactants. This leads to a dynamic equilibrium between bound and unbound ligands, enabling
facile ligand loss.[20] In addition, oleylamine itself can also accelerate the degradation of the
nanocrystals by coordinating the lead species (Pb-oleate, PbX2) and ultimately dissolving the
Moving beyond the use of oleylamine is challenging because this ligand is presently
relied upon to solubilize the lead halide precursor. We thus turned instead to Cs-oleate (CsOA)
and Pb-oleate (PbOA2) and searched for a new halide source. We were inspired by ligand
provide stable iodide passivation of metal rich QD surfaces through the cleavage of lead-
provides predictive pathway for the reaction between CsOA and PbOA2 with quaternary
Recently, Wei et al. reported a room temperature synthetic method based on carboxylic
acid capped CsPbBr3 PQDs and further applied post-synthetic anion exchange techniques to
form CsPbX3 PQDs (X= Cl, Br, I)[26]. However, PQDs show degraded PLQY properties within
2-3 days and, surprisingly, suffered from lower PLQY for above room temperature reactions.
Here we carry out an extensive study to employ OA capped supported by deep experimental
tetraoctylammonium halides (TOAX) for preparation of OA capped CsPbX3 PQDs without the
need of post-anion exchange methods. The PQDs show PLQY of 70%, narrow emission spectra,
and enhanced colloidal stability. We show that these PQDs are more stable upon purification
with polar solvents, an advance that we attribute to stronger ligand attachment. We further
fabricate red, green, and blue (RGB) PQD LED using first time solution-processed polymer-
based hole transport layers in an inverted LED structure for PQDs. Green and blue LEDs show
a threefold increase in performance for green, and tenfold for blue LED efficiencies compared
to prior related reports for amine/ammonium capped cross-linked PQDs.[27] We further explore,
using ultrafast spectroscopy, the effects of photocharging and fast Auger recombination in
4
PQDs. We identify these as the key factors that need to be addressed to achieve further
To understand the reaction mechanism, its limiting steps and possible ways to control
growth, we carried out density functional theory (DFT) molecular dynamics simulations of the
nucleation and crystal growth kinetics starting from the chosen precursors: CsOA, Pb(OA)2,
TOABr (for simplicity, the acetate molecule is shown in the figure instead of oleic acid). In the
first step of the reaction, we find that Cs and Pb oleates react readily with Br anions, since Cs
and Pb cations are large and prefer higher coordination than OA can provide (Figure 1, step
a). However, the resulting (PbOA2Br) clusters do not react further as they become electronically
saturated, even though the size of the cation could allow for higher coordination. In contrast,
both PbBr2 and (PbOABr2) are more reactive and form polymeric chains thanks to the ability
of Br- to coordinate to more than one lead ion (Figure 1, step b). The exchange of the oleate
ion for a bromide anion therefore becomes the limiting step for further growth of the nuclei. It
is known that the detachment of the oleate anion from the surface of the lead cation is a highly
unfavorable unless a proton participates and assists the detachment.[12] Similarly, detachment
of oleate ligands continues to be the limiting step at every stage of the nanocrystal growth
(Figure 1, step c). Instead of a proton, we use TOA cation to facilitate the desorption of OA
and to control the nanocrystal growth. The use of TOA eliminates formation of reversible
are used there can be reversible exchange between alkylammonium to alkyamine. Therefore,
5
In a typical reaction, Cs-acetate, Pb-acetate, ODE, oleic acid are placed in the flask and
heated to 120°C until CsOA and PbOA2 are formed under vacuum. Then flask is placed under
nitrogen and temperature is lowered to 75°C to inject TOAX source. Injection of TOABr at
75°C into a CsOA and PbOA2 containing mixture resulted in an immediate change in the color
of the solution from clear transparent to green, indicating the formation of CsPbBr3 PQDs.
Moreover, the solution remained clear longer than conventionally prepared PQDs, indicating
that the oleic acid capped dots show enhanced colloidal stability (Figure S1). This was also
confirmed during purification of the PQDs by attempting to crash the crude solution without
any anti-solvents. To our surprise, oleic acid capped dots do not precipitate without the
spontaneously from solution.[13,18,19] CsPbBr3 and CsPb(Br,Cl)3 PQDs showed high stability;
however, CsPb(Br,I)3 PQDs do become unstable over time. This may be attributed to their
sensitivity to moisture. The synthesis of blue and red photoluminescent PQDs is achieved by
the incorporation of mixed halide anions and carried out in a similar fashion to CsPbBr3
The absence of oleylamine also accelerates the growth reaction of PQDs. For example,
the growth of average CsPbBr3 (~8 nm) PQDs requires ~150°C reaction temperature, whereas
in the absence of oleylamine, similar-sized PQDs were formed at 75°C. We attributed the lower
reaction temperature to the absence of oleylamine, already known by its strong coordination
that reduces the reactivity of PbX2. This inhibiting effect had also been reported for syntheses
of InP quantum dots when oleylamine was utilized.[28] We further studied the effect of
S2). We find that addition of increasing quantities of oleylamine causes a blue shift, indicating
6
Fourier transform infrared (FTIR) spectra of as-synthesized PQDs show the presence of
OA (COOH) and oleate species (COO-) (Figure 2b). COO- stretching confirmed the binding
of Pb oleate species on PQD surfaces at 1525 and 1553 cm-1 (Figure S3).[29] These signals
confirm the bond chelating and bridging from PbOA2 on the surfaces of oleic acid capped PbS
COO- groups, and their solutions possessed a lower quantity of free OA. This allowed us to
remove most excess ligands without affecting the colloidal stability. The PQD PL peak
positions are not shifted (Figure 2c). In conventional oleylamine/oleic acid capped PQDs, a
similar degree of purification inevitably led to a red shift of PL, indicating growth or fusion of
those PQDs.[19] X-ray diffraction (XRD) measurements confirm the cubic perovskite crystal
structure of RGB PQDs with peak shifts consistent with the formation of alloys (Figure 2d).
and ammonium ligands on the surface of PQDs after one- and two-time washing. Both amine
and ammonium species are present on the surface of conventional PQDs even after two washing
steps. This resonates with the conclusions of Hens, Kovalenko and co-workers regarding ready
and reversible proton transfer between OA and amine which accelerates the desorption of
degradation of PQDs.[20,21,31] High resolution XPS N1s spectra of our solely-oleic-acid capped
CsPbBr3 PQDs do not show any detectable nitrogen after one and two washing steps (Figure
quantum dots confirms the CsPbBr3 perovskite structure (Figure 3a). The lattice spacing (5.8
Å) corresponds to the {110} lattice planes. HR-TEM analysis show that average particle size is
between 7-10 nm, confirming the quantum confinement effect (Figure S5). Interestingly, the
7
reaction carried out at 75°C does not form platelets, a finding that had previously been reported
Ligand detachment during washing steps enabled PQDs to attach firmly onto
hydrophilic substrates. An inverted LED device architecture was chosen in which the perovskite
quantum dot layer was sandwiched by a TiO2 electron transport layer and by a poly(9,9’-
dioctylfluorence) (F8) hole transport layer. The band diagram of the devices, shown in Figure
3b, indicates the well-aligned band levels between PQDs and CTLs. Cross-section scanning
electron microscope (SEM) imaging revealed that the overall thickness of the device is less than
200 nm (TiO2: 10-15 nm, active perovskite layer: ~10 nm, F8: 15 nm, MoO3/Au anode: ~100
nm) (Figure 3c). Atomic force microscopy (AFM) confirmed the low surface roughness (Rq)
of the active layer (on top of TiO2/ITO substrate) was around 2 nm (Figure 3d).
corresponding types of perovskite quantum dots (red: Br/I mixed; green: pure Br; blue: Br/Cl
mixed). Compared to the PL spectra (Figure 4a), no significant EL wavelength shift was
observed in RGB devices (EL peak at ~650 nm, 510 nm, 495 nm respectively). Blue and green
EL signals are symmetric without noticeable peak broadening (FWHM of RGB devices are 35,
25 and 21 nm, respectively), indicating that the luminescence qualities of the active perovskite
Device turn-on voltages were between 2.6 and 4 V depending on the PQD type (Figure
4d). The corresponding peak EQE values are 0.05%, 0.325% and 0.075% for RGB devices,
respectively (Figure 4c). Green and blue LEDs show a threefold increase in performance for
green, and tenfold for blue LED efficiencies compared to prior related reports for
amine/ammonium capped cross-linked PQDs. The relatively low EQE value of the blue-
emitting device arises from inefficient charge blocking by the F8 layer. The conduction band
8
of perovskite was moved closer to the LUMO of F8, which is also reflected in the device current
to date and device architectures in Table S1. All published PQD-LEDs utilize evaporated
electron or hole transport layers. Here, we report a new device architecture that utilizes a
to solution processing. CsPbX3 PQDs provide LED device performance comparable with
previous reports (Table S1). The range of the luminance was 30 - 930 Cd/m2, comparable to
previous PQD LEDs (Figure 4d).[27] It was, however, achieved at notably lower voltage (R: 2.6
V, G: 2.8 V, and B: 4.1 V). While almost the same brightness was found from the blue and
green devices, we noticed the red-emitting devices were dimmer: their lower performance may
A possible reason for the limited EQE in PQD-based LEDs is the strong influence of
uncontrolled charge injection, and consequent trion decay.[33] To verify the strength of Auger
solution and films. Figure 5 shows transient absorption (TA) results for the green-emitting
PQDs with biexction lifetime of 38 ± 5 ps. To verify that the fast decay is indeed due to
biexciton formation, we characterized its amplitude as a function of the pump intensity (see
Figure S6), finding that it follows Poisson statistics expected for biexctions. A slower decay of
about 180 ps also emerges as the pump intensity increases, indicating the presence of ionized
PQDs and trion decay.[34] These values agree with the values recently reported for similar
CsPbBr3 PQDs.[35,36] For the sample investigated in this work, photo-ionization, and consequent
trion formation, accounts for less than 10% of the measured signal. However, when comparing
the TA results for PQDs in solution and in a spin-cast films we observed a stronger influence
9
process.[37] This is suggestive that charging could be one factor that limits the devices' EQE.
Considering the PL and trion lifetimes, we can estimate that, if the device is dominated by
charged species, the maximum EQE would be near 3%. This suggests that it is imperative to
3. Conclusion
We developed an amine-free synthesis for PQDs stabilized solely by oleic acid, enabled
by the choice of a novel halide precursor. Oleic acid capped PQDs showed improved colloidal
stability and provided high stability against polar solvents during purification. This allows
solution-processed conductive PQD films with low organic content and increased stability. We
report a new LED device architecture by utilizing solution-processed polymer based hole
transport layer with highly comparably RGB LED performances. Further optimization of
synthesis and device fabrication of perovskite quantum dots is the subject of ongoing
investigation, in particular, the core-shell structures to reduce the Auger recombination losses.
Supporting Information
Supporting Information is available from the Wiley Online Library or from the authors.
Acknowledgements
E.Y., Z.Y. and O.V contributed equally to this work. This publication is based in part
and Technology (KAUST), by the Ontario Research Fund - Research Excellence Program,
and by the Natural Sciences and Engineering Research Council of Canada (NSERC). E.Y.
fellowship. J.A.C. and L.A.P. acknowledge the financial support from FAPESP (Project
10
number 2013/16911-2). A.F.N acknowledge FAPESP, CNPq and INEO. The authors thank
Dr. Y. Zhao for useful discussions. The authors thank L. Levina, E. Palmiano, R. Wolowiec,
and D. Kopilovic for their technical help over the course of this study.
References
12
Figure 1. Density functional theory molecular dynamics simulation of CsPbBr3 nucleation and
growth steps (for simplicity, the synthesis is shown with acetate group instead of oleate). a)
Dissociated ammonium bromide ions form complexes with CsOA and PbOA2. b) Further
reaction between these complexes requires one of the OA- being replaced with Br-. c) Br
13
Figure 2. Optical and structural characterization of CsPbX3 (X = Cl, Br, I) PQDs. a) Absorption
and PL spectra of RGB CsPbX3 PQDs color coded with the corresponding color b) FTIR spectra
of unwashed, once washed and twice washed CsPbBr3 PQDs. c) PL spectra of unwashed and
twice washed CsPbBr3 PQDs showing identical PL spectrum. d) X-ray powder diffraction of
14
Figure 3. a) High resolution spectrum of CsPbBr3 PQDs, inset showing d-spacing calculation
for single crystal. b) Device band diagram, c) Cross sectional SEM image of PQD-LED devices
15
Figure 4. Device characterization of RGB PQD-LEDs. a) RGB photoluminescence (dashed
lines) and electroluminescence spectra (straight lines). b) Current density vs. Voltage (J-V)
curve of PQD LED devices. c) Radiance vs. voltage Diagram for RGB PQD-LED. d) EQE vs.
16
Figure 5 a) Transient absorption spectra for green emitting PQDs in toluene solution for several
pump intensities (inset: shows the multiexciton dynamics at high excitation energy (<N> =
2.2)). b) Comparison between the transient absorption spectra of PQDs in solution and film.
17
The table of contents entry
We report a new synthetic method that enhances the colloidal stability of perovskite quantum
dots by using solely oleic acid ligands. We use quaternary alkylammonium halides as
precursors, eliminating the need for oleylamine.We fabricate inverted red, green and blue
LEDs using solution-processed polymer-based hole transport layers for the first time, allowed
for by the higher robustness of oleic acid capped perovskite QDs against solution processing.
The LEDs exhibit a threefold and tenfold improvement in EQE for green and blue,
respectively, compared to prior reports for amine/ammonium capped perovskite QDs..
Emre Yassitepe,, Zhenyu Yang, Oleksandr Voznyy, Younghoon Kim, Grant Walters, Juan
Andres Castañeda, Pongsakorn Kanjanaboos, Mingjian Yuan, Xiwen Gong, Fengjia Fan, Jun
Pan, Sjoerd Hoogland, Riccardo Comin, Osman Bakr, Lazaro A. Padilha, Ana F. Nogueira,
Edward H. Sargent*
Amine-free Synthesis of Cesium Lead Halide Perovskite Quantum Dots for Efficient
Light-Emitting Diodes
ToC figure
18
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013.
Supporting Information
Emre Yassitepe,, Zhenyu Yang, Oleksandr Voznyy, Younghoon Kim, Grant Walters, Juan
Andres Castañeda, Pongsakorn Kanjanaboos, Mingjian Yuan, Xiwen Gong, Fengjia Fan, Jun
Pan, Sjoerd Hoogland, Riccardo Comin, Osman Bakr, Lazaro A. Padilha, Ana F. Nogueira,
Edward H. Sargent*
Chemicals
All chemicals are obtained from Sigma-Aldrich unless noted otherwise. Materials: oleic acid
(OA, tech. 90%), 1-octadecene (ODE), cesium acetate, lead acetate, tetraoctylammonium
bromide (TOABr), tetraoctylammonium chloride (TOACl), octylamine, hydrogen iodide,
toluene, ethanol anhydrous, octane, acetone, distilled in glass (Caledon).
Tetraoctylammonium iodide (TOAI) was purchased from TCI chemicals.
1 mmol of Cs acetate, 2 mmol of Pb acetate is placed in a flask with 2 ml oleic acid and 5 ml
1-ODE mixture. The flask is kept under vacuum and heated to 100°C to form CsOA and PbOA.
For CsPbBr3 PQD synthesis, 2 mmol TOABr source is dissolved in anhydrous toluene and
swiftly injected into the reaction flask at 75°C. After 5 seconds, the heating source is removed
and allowed to cool by itself. For CsPb(Br,I)3 , 1mmol (TOABr:TOAl, 2:1 in toluene) and
CsPb(Br,Cl)3 (TOABr:TOACl, 2:1 in Toluene) was injected at 75°C. However for CsPb(Br,I)3
synthesis the reaction quenched with ice-water bath and 1-butanol is added to prevent rapid
decomposition of PQDs. CsPbBr3 and CsPb(Br,Cl)3 PQDs are purified by hexane (15 ml) and
acetone (30 ml) with centrifuge. An additional wash can be performed using the similar
procedure. For CsPb(Br,I)3 dots the purification is carried out by only 1-butanol.
19
is fabricated by a two-step method: (i) the initial layer was deposited at 150oC using atomic
layer deposition (ALD) (Cambridge Savannah S100 ALD system) using tetrakis
(dimethylamido) titanium (IV) and water as precursors; (ii) the film was further treated by
TiCl4 aqueous solutions (40 mM) at 70oC for 30 minutes, followed by washing with DI water,
drying by N2 flow, and finally annealed at 400oC for 1 hour. After cooling down, substrates
are stored in a nitrogen-filled glovebox for further use. Perovskite quantum dot ink in octane
was spin-coated onto the TiO2/ITO substrate at room temperature at 2000 rpm for 30 seconds.
The F8 chlorobenzene solution (10 mg/mL) is annealed at 75oC under nitrogen atmosphere
and spin-coated onto the perovskite quantum dot layer at a spin speed of 3000 rpm for 60
seconds to form a uniform hole transport layer. The top electrode, consisting of 6 nm of MoO3
and 100 nm of Au, is deposited by thermal evaporation at a pressure of <1 × 10-6 Torr. Each
ITO substrate (2.5 cm × 2.5 cm) was patterned to yield eight devices, each with an area of 3.1
mm2.
PL and EL measurement
Photoluminescence measurements were performed using a Horiba Fluorolog Time Correlated
Single Photon Counting system with photomultiplier tube detectors. A monochromatized Xe
lamp and pulsed laser diodes (442 nm) were used as excitation sources for steady-state and
transient measurements, respectively. Absolute PLQE measurements were done in a Quanta-
Phi integrating sphere according to the standard method published elsewhere [1] For EL
measurement, devices are characterized using a Keithley 2410 source meter. Under a range of
forward bias voltages, the EL spectra are collected through a set of lenses focused on an
optical fiber and connected to the visible light spectrophotometer (Ocean Optics, USB2000).
Transient Absorption
20
Transient absorption was performed in PQDs solution in 1 mm spectroscopy grade cuvette, or
in films prepared by spin coating. Excitation was chosen at 3.1 eV with 100 fs pulses at 1 kHz
repetition rate. Probe was selected from an optical parametric amplifier, and it was set near the
position of the first absorption peak. The absorption cross section was measured at 3.1 eV by
using a Poisson statistic to fit the saturation of the amplitude at long delay (~200 ps) as shown
in Fig. S4a. For that, we assume that every PQD that has absorbed at least one photon is left
with only one exciton at 200 ps, this way, the amplitude is given by 𝐵 = 𝐵𝑚𝑎𝑥 (1 − 𝑒 −〈𝑁〉 ),
where Bmax is the maximum amplitude measured and depends on the experimental conditions.
〈𝑁〉 is the average number of photons absorbed per PQD and is given by 〈𝑁〉 = 〈𝑁〉3.1𝑒𝑉 𝜎3.1𝑒𝑉 ,
〈𝑁〉3.1𝑒𝑉 is the number of photons at 3.1 eV in the laser pulse per cm2 (experimentally measured
based on the laser power and spot size) and 𝜎3.1𝑒𝑉 is the PQD absorption cross section at 3.1
eV. Using the same cross-section obtained in Fig. S4a, we could fit the amplitude of the fast
component using the Poisson statistic for biexcitons 𝐴 = 𝐴𝑚𝑎𝑥 (1 − 𝑒 −〈𝑁〉 (1 + 〈𝑁〉)). This
verifies that the 38 ps decay is due to biexciton. We also observe the presence of trions, but
their contribution in solution is small (less than about 10%), but the PQDs becomes more prone
to photo-ionization when deposited in film.
a) b)
21
Figure S2- The effect of 0.2 ml oleylamine addition to as prepared oleylamine- oleic acid
CsPbBr3 quantum dots over 1 hr.
Increasing time
PL Intensity (a.u)
Figure S3 – FTIR spectra (1400-1700 cm-1) of unwashed, once washed and twice washed
CsPbBr3 PQDs
22
Figure S4. High resolution N 1s and Pb 4f spectrum of a) Conventionally synthesized PQDs
after 1 and 2 washing steps b) PQDs synthesized via oleic acid and alkylammonium halides
after 1 and 2 washing steps
23
Figure S5 – Particle size distribution of CsPbBr3 PQDs calculated from HR-TEM image. The
average particle size is found to be 7-10 nms.
Figure S6. Long delay amplitude (a) and the amplitude of the fast decay component (b). Data
was fitted using Poisson statistic for single exciton (a) and biexciton (b) obtaining the cross
section at 3.1 eV of 1.4 x 10-14 cm2.
24
Table S1 – MAPbX3, CsPbX3 PQD-LED performance chart with device configurations
Lumi
nous Lumin
Turn- Max. Pow ous
Wavele
Refere on Lumina EQE er Efficie
ngth Notes
nce Volta nace (%) Effici ncy
(nm)
ge (V) (Cd m-2) ency (Cd A-
(lm 1)
W -1)
J.
Song,
CsPbBr3 QD as active material,
et al., 455, 5.1, 0.07, 0.07, 0.14,
Architecture:
Adv. 516, 4.2, 946 0.12, 0.18, 0.43,
ITO/PEDOT:PSS/Perovskite/TPBI/
Mater. 586 4,6 0.09 586 0.08
LiF/Al
,
2015[2]
Y.
Ling,
MAPbBr3 nanoplatelet as active
et al.,
material, Architeture:
Adv. 530 3.8 10590 0.48 1.0 \
ITO/PEDOT:PSS/Perovskite/PVK
Mater.
:PBD/BCP/LiF/Al
,
2016[3]
W.
3.05
Deng, 7.8 3.03
(only
et al., (only (only MAPbBr3 QD as active material,
445, 2673, 1.38, gree
Adv. green green Architecture:
525, 2398, 1.06, n
Funct. was was ITO/PEDOT:PSS/Perovskite/TPBi/
640 986 0.53 was
Mater. report report LiF/Ai
repor
, ed) ed)
ted)
2016[4]
X.
CsPbBr3 QD as active material,
Zhang
Architecture:
et al.,
516 3.5 1377 0.06 \ 0.19 ITO/PEDOT:PSS/poly-
Nano
TPD+PFI/Perovskite/
Lett.,
TPBi/LiF/Al
2016[5]
G. Li,
et al., 0.007 CsPbX3 QD as active material,
480, 2.8, 8.7,
Adv. , Architecture:
523, 2.0, 2335, \ \
Mater. 0.19, ITO/ZnO/Perovskite/TPB/MoO3/A
698 1.4 206
, 5.7 g
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J.
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et al.,
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This 750,
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25
References
26