Article

Cite This: J. Am. Chem. Soc. 2018, 140, 8887−8894 pubs.acs.org/JACS

Hierarchical Arrays of Cesium Lead Halide Perovskite Nanocrystals

through Electrophoretic Deposition
Vikash Kumar Ravi,# Rebecca A. Scheidt, Jeffrey DuBose, and Prashant V. Kamat*
Radiation Laboratory and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556,
United States
*
S Supporting Information

ABSTRACT: The suppression of halide ion exchange between CsPbBr3

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and CsPbI3 nanocrystals achieved through capping with PbSO4−oleate

has enabled us to deposit different perovskite nanocrystals as aligned
arrays on the electrode surfaces without intermixing of species. The
electrophoretic deposition of PbSO4−oleate-capped CsPbX3 (X = Cl, Br,
I) nanocrystals suspended in hexane solution on mesoscopic TiO2 films
allows the design of controlled architecture with single or multiple layers
of perovskite films. The hierarchy in the assembly of these nanocrystals is
seen first through the linearly organized nanocrystals in hexane followed
by the deposition of larger linear rods ∼500 nm in length. Since most of
the photophysical properties of nanocrystals are retained in these aligned
arrays, we can design films with tunable luminescence including white
color. The electrophoretic deposition of layered films of perovskites in a
controlled fashion opens up new ways to design tandem perovskite solar cells and tunable display devices.

■ INTRODUCTION
Metal halide perovskites have gained prominence in multi-
disciplinary research areas because of their interesting
optoelectronic and photovoltaic properties.1 Of particular
interest is cesium lead halide (CsPbX3) nanocrystals, which
can be prepared by a simple hot injection method.2 The ease of
synthesis has enabled researchers to explore size- and
composition-dependent photophysical properties of
CsPbX3.3−10 For example, the ratio of Cl:Br and Br:I, which
dictates the bandgap of metal halide perovskites, has been used
to tune the absorption and emission properties across the
entire visible region.3 However, these CsPbX3 nanocrystals are
extremely sensitive to the chemical environment and undergo
morphological changes. For example, a CsPbBr3 nanocrystal
suspension exposed to dodecyl dimethylammonium bromide
results in the formation of 2D nanosheets.11 As the Cs+ ions
are exchanged with the alkyl ammonium ions, the cubic
nanocrystals undergo dissolution and reconstruction to form 2-
D CsPb2Br5 nanosheets. This instability in turn poses a
problem for their utilization in practical applications.12−16
Another interesting property of CsPbX3 nanocrystals is to
undergo halide ion exchange when in contact with other halide
ions to produce mixed halide species.3,17,18 Interestingly, this
halide ion exchange process is reversible, and the original
composition can be restored by exposing the nanocrystals to
the original halide ions. Whereas such ease of halide ion
exchange allows one to create a gradient structure within the
CsPbBr3 film4 or achieve tunable emission,19 it also poses a
challenge to create films or suspensions with two or more
halide nanostructures that exist simultaneously. As shown in
our earlier study, if two different CsPbX3 (X = Cl, Br, or I)
nanocrystal suspensions are mixed, the halide exchange
between two different nanocrystals produces a mixed halide
nanocrystal suspension.20
The movement or exchange of halide ions in metal halide
perovskites thus becomes an interesting property to probe
their structural and optical properties. The halide ion mobility
within perovskite films in the dark as well as under light has
been a topic of debate because of its direct influence on the
photovoltaic performance.12,21−25 Correlated wide-field PL
microscopy and impedance spectroscopy are employed to
observe real-time movement of halide ions in perovskite films
through spatial and temporal evolution of PL inactive areas
under external applied electric fields.26 The kinetics of halide
ion movement during steady state light irradiation has been
monitored through spectral changes to elucidate the phase
segregation effect in mixed halide films.21,27−29 Efforts have
been made to restrict such halide ion movement in mixed
halide films using self-assembled long-chain organic ammo-
nium capping layers on nanometer-sized mixed halide
perovskites.30 Yet, such efforts do not provide full protection
against halide ion exchange or photoinduced phase segrega-
tion.
We have recently shown that CsPbX3 nanocrystals can be
stabilized against halide ion exchange by capping with PbSO4−
oleate without altering their photophysical properties.20 The
ability to suppress the halide ion exchange in these capped
Received: May 7, 2018
Published: June 21, 2018

© 2018 American Chemical Society 8887 DOI: 10.1021/jacs.8b04803

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nanocrystals raises the possibility to utilize them in tandem
architecture.31,32 Another interesting property of these
PbSO4−oleate-capped nanocrystals is their ability to assemble
in a linear fashion resembling the morphology of a peapod.33,34
The obvious question is whether one can assemble these
peapod nanostructures as films on electrode surfaces. We now
present here an electrophoretic deposition method to assemble
PbSO4−oleate-capped CsPbX3 peapods on mesoscopic TiO2
films as an orderly aligned array. The photophysical properties
of single and layered films of different lead halide perovskite
arrays are discussed.
■ EXPERIMENTAL METHODS
Chemicals. Cesium carbonate (Cs2CO3, Alfa Aesar, 99.9%), 1-
octadecene (ODE, Sigma-Aldrich, 95%), oleylamine (OAm, Sigma-
Aldrich, 70% technical grade), oleic acid (OA, Sigma-Aldrich, 90%
technical grade), hexane (Sigma-Aldrich, 95% anhydrous), methyl
acetate (MeOAc, Sigma-Aldrich, 99.5% anhydrous), tetrabutylammo-
nium hydrogen sulfate (TBAHS, Acros, 98%), lead(II) chloride
(PbCl2, Sigma-Aldrich, 99.999%), lead(II) bromide (PbBr2, Sigma-
Aldrich, 99.999%), lead(II) iodide (PbI2, Sigma-Aldrich, 99.999%),
acetone (Sigma-Aldrich, ≥99.5% ACS reagent), and chloroform
(CHCl3, Fischer Scientific, 99.9% HPLC grade) were employed.
Preparation of CsPbX3 Nanocrystals and PbSO4−Oleate-
Capped Nanocrystals. A cesium carbonate stock solution was
prepared by dissolving 0.4 g of Cs2CO3 in 20 mL of 1-octadecene at
150 °C and then stored in a vial under inert conditions for later use.
PbX2 (0.94 mmol of PbCl2, PbBr2, or PbI2) precursor was placed in a
three-necked round-bottom flask with 30 mL of 1-octadecene. It was
then degassed by placing the flask under alternating vacuum and
nitrogen gas to get rid of dissolved oxygen and moisture at 120 °C.
After that, 2.5 mL each of oleic acid and oleylamine were added, and
the temperature was increased to 150 °C in order to completely
dissolve the lead halide precursor. Finally, the preheated (100 °C)
cesium oleate solution was injected at 170 °C, and the reaction was
quickly quenched via an ice bath after 5 s. The crude nanocrystals
were then washed twice with methyl acetate and finally redispersed in
hexane for further use. For the capping of CsPbX3 nanocrystals with
PbSO4−oleate, PbSO4 clusters were prepared by following an earlier
reported method:33 0.4 mL of PbCl2 (139 mg in 8 mL of oleylamine),
0.2 mL of tertiary butyl hydrogen sulfate (424.4 mg in 10 mL of
acetone), and 0.4 mL of oleic acid were mixed in 10 mL of chloroform
and sonicated for 5 min. The mixture was precipitated by 30 mL of
ethanol, and the precipitate redissolved in 2 mL of chloroform. The
PbSO4 clusters were then added to as-prepared CsPbX3 nanocrystals
and left undisturbed for 12 h. The mixture was then centrifuged, and
the precipitate dissolved in hexane for further use.
Deposition of PbSO4−Oleate-Capped CsPbX3 on FTO/TiO2
Electrodes. TiO2 was coated on a fluorine-doped tin oxide (FTO)
substrate by a doctor blading method and then annealed at 90 °C for
1 h followed by 500 °C for 1 h. Two electrodes were then connected
to a dc supply and dipped into a dispersion of PbSO4−oleate-capped
CsPbX3 nanocrystals. Depending on the time or the voltage applied,
the film thickness (number of deposited nanocrystals) was controlled.
Characterization. UV−vis spectra were recorded on a Cary 50
Bio UV−vis scanning spectrophotometer. Emission spectra were
recorded using a Horiba Jobin Yvon Fluorolog 3 spectrophotometer.
Time-correlated single photon counting (TCSPC) measurements
were carried out using a Horiba Jobin Yvon single photon counting
system. A 370 nm NanoLED laser was used for excitation of the
sample. Transmission electron microscopy (TEM) images were
recorded using a JEOL JEM 2011 transmission electron microscope at
200 kV. Top-down scanning electron microscopy (SEM) images were
recorded on a Magellan 400 scanning electron microscope. Cross-
sectional SEM images as well as energy-dispersive X-ray spectroscopy
(EDX) were performed on a Helios NanoLab Dual Beam 600.
Transient spectra were recorded on a Clark MXR 2010 chirped
pulse amplifier laser system (1 mJ/pulse, 1 kHz rep rate, fwhm = 150
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fs). The 775 nm fundamental beam was split using a 95/5 beam
splitter where the 95% became the pump beam and the 5% became
the probe. The pump was passed through a frequency doubler to
obtain the second harmonic of 387 nm. The probe was passed
through a CaF2 crystal to generate a white light supercontinuum. For
all measurements, the pump power density was kept at 4 μJ/cm2.
Helios software from Ultrafast Systems was used to collect and
analyze the data.
■ RESULTS AND DISCUSSION
Electrophoretic Deposition. The electrophoretic deposi-
tion of semiconductor and metal nanoparticles has been
employed by our group and others.35−38 This deposition
method provides a convenient way to deposit one or more
layers of nanocrystals within the mesoscopic TiO2 film.
However, pristine CsPbX3 nanocrystals prepared in hexane
do not carry sufficient charge to allow deposition by
electrophoresis. Interestingly, PbSO4−oleate-capped CsPbX3
peapods carry a net negative charge and can be driven toward
the positive electrode when subjected to a dc electric field.
The PbSO4−oleate-capped CsPbCl3, CsPbBr3, and CsPbI3
nanocrystals were prepared using the method described
earlier.20,33 Additional details of the synthesis are presented
in the Supporting Information. The absorption and emission
properties of CsPbCl3, CsPbBr3, and CsPbI3 nanocrystal
suspensions in hexane are presented in Figure S1 and the
emission quantum yields are presented in Table S1
(Supporting Information).
For electrophoretic deposition we transferred 3 mL of each
nanocrystal (peapod) suspension into a quartz cuvette. The
mesoscopic TiO2 film on FTO and unmodified FTO
electrodes were inserted in parallel with a gap of ∼6 mm.
The electrodes were connected to a dc power supply (TiO2-
coated FTO connected to the positive terminal), and a 100 V
dc electric field was applied (Figure 1). With increasing time,
Figure 1. Schematic diagram illustrating the principle of electro-
phoretic deposition of PbSO4−oleate-capped CsPbX3 nanocrystals
from hexane solution onto FTO/TiO2 films.
the nanocrystals suspended in the solution moved toward the
positive electrode and were assembled onto the TiO2 film. The
film became more colored as nanocrystals were deposited onto
the TiO2 film. This is in contrast with the deposition solution,
which lost absorbance over time, indicating that the NCs were
leaving the solution.
Figure 2A shows the three different configurations of the
CsPbBr3 and CsPbI3 films prepared in this study using
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Figure 2. (A) Three different electrode configurations and (B) the absorbance spectra of FTO/TiO2 films following the deposition of PbSO4−
oleate-capped CsPbBr3 and CsPbI3 nanocrystals. (C and D) Changes in the solution absorbance with time corresponding to the number of
nanocrystals deposited on the electrode. This was monitored at 500 nm (C) and 670 nm (D) for CsPbBr3 and CsPbI3, respectively. The typical
deposited amounts were 0.8 nmol/cm2 CsPbBr3 and 0.9 nmol/cm2 CsPbI3 nanocrystals.

Figure 3. Transmission electron micrographs of (A) CsPbCl3, (B) CsPbBr3, and (C) CsPbI3 nanocrystals capped with PbSO4−oleate in hexane.
Scanning electron micrographs with low (D, E, F) and high (G, H, I) magnification of electrophoretically deposited (D, G) CsPbCl3, (E, H)
CsPbBr3, and (F, I) CsPbI3 nanocrystals on TiO2 films.

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Scheme 1. Hierarchical Assembly of CsPbX3 Nanocrystalsa
a
Illustration of alignment of cesium lead halide nanocrystals following PbSO4−oleate capping in hexane and bundled arrays on the electrode
surface following electrodeposition.
Figure 4. (A and B) Top view and (C and D) cross-sectional view of CsPbBr3 film (A, C, E) and CsPbBr3/CsPbI3 layered films capped with
PbSO4−oleate (B, D, F) deposited on mesoscopic TiO2 film using electrophoretic deposition. The compositions of the film along the cross section
of the two films are presented in panels E and F.
electrophoretic deposition. The absorption spectra of these
three electrodes are shown in Figure 2B. We also prepared
films of CsPbCl3 nanocrystals. For the sake of clarity, we have
included the absorption and emission properties of the
CsPbCl3 species in the Supporting Information (Figure S2).
The spectra a and b in Figure 2B show the absorption
corresponding to the individual perovskite films of PbSO4−
oleate-capped CsPbBr3 and CsPbI3 nanocrystals, respectively.
The spectrum c corresponds to the bilayer film of the two
different nanocrystals deposited sequentially. These films,
which show an additive absorbance feature, remain stable
over an extended period of time under ambient conditions.
Figure 2C and D show the rate of deposition of nanocrystals
onto the electrode surface as monitored from the disappear-
ance of solution absorbance. The difference absorbance of the
suspension was used to determine the amount of nanocrystals
deposited on the electrode surface. The absorption spectra
recorded during electrophoretic deposition of these two
samples are included in the Supporting Information (Figure
S3). As can be seen from the traces in Figure 2C,D, within
about 300 s it is possible to drive the nanocrystals from
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solution onto the electrode surfaces. This deposition depend-
ence on time allows us to control the amount of nanocrystals
deposited on the electrode surface. The total amount of
nanocrystals deposited on the electrode surface during
deposition time was 0.8 nmol/cm2 of CsPbBr3 and 0.9
nmol/cm2 of CsPbI3, respectively. The electrophoretic method
of deposition of perovskite nanocrystals is quick and less
tedious than conventional spin coating9,39 or vapor deposi-
tion40 methods. The convenience of achieving desired film
thicknesses with ease allows deposition of multiple layers of
different perovskite nanocrystals.
Film Morphology. As evidenced from TEM, the process of
capping CsPbX3 nanocrystals with PbSO4−oleate in hexane
makes them assemble in a linear fashion. Figure 3A−C show
the linear assemblies of three different CsPbX3 nanocrystals.
Although the exact reason for the linear assembly of
nanocrystals resembling a peapod architecture after the
addition of PbSO4oleate is not fully understood, it has been
proposed that the capping layer promotes this process.20,33 In
solution, we observe such assemblies of a few hundred
nanometers in length resembling a peapod architecture. The
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Figure 5. (A) Time-resolved transient absorption spectra recorded following 387 nm laser pulse excitation of sequentially layered PbSO4−oleate-
capped CsPbBr3/CsPbI3 film. (B and C) Absorbance−time profiles monitored at 530 and 650 nm corresponding to the exciton bleach recovery of
CsPbBr3 and CsPbI3 in the layered film, respectively. The transient spectra of PbSO4−oleate-capped CsPbBr3 and CsPbI3 are shown in the
Supporting Information (Figure S5).
capping procedure also seems to affect the size of these
nanocrystallites, as we observe a wider range of size
distribution of cubic nanocrystallites within the peapod
structure.
The obvious question then would be whether electro-
phoretic deposition onto the electrode surface preserves these
structures without degradation or loss of capping. Panels in
Figure 3 show SEM images (D−I) of CsPbX3 films deposited
on a TiO2 film at two different magnifications. Electrophoreti-
cally deposited films of all three CsPbX3 nanocrystals showed
similar morphology of well-aligned arrays on the electrode
surface. Both low (D−F) and high (G−I) magnification SEM
images in Figure 3 confirm the assembly of nanocrystals in the
form of 400−500 nm long rods. Interestingly, the shape of the
assembled CsPbX3 nanocrystals remains linear, and they are
packed closely in peapod arrays on the top of the TiO2 film. A
closer look at the higher magnification image suggests that
several of the linear assembled nanocrystal in solution bundle
up in an organized fashion to produce larger rods. Given the
predominance of PbSO4 shells, we could not view the
individual nanocrystallites buried within these larger nanorod
arrays. Scheme 1 depicts the initial alignment of PbSO4−
oleate-capped nanocrystals in solution and their bundling to
form larger nanorod secondary arrays on the electrode surface.
It is possible that charge neutralization of the peapod assembly
near the electrode surface promotes their aggregation and
forms larger rods as they get deposited onto the electrode
surface.
Layered Film Architecture. These perovskite films show
good stability in hexane, and the deposition cycle can be
repeated to obtain two or more layers of the CsPbX3 films. We
used this approach to successively deposit two perovskite
layers, viz., first deposition of a layer of CsPbBr3 nanocrystals
followed by the deposition of CsPbI3 nanocrystals. The top-
view SEM images are shown in Figure 4A and B, respectively.
In these bilayer films, following the successive deposition, the
linear assembly feature is maintained for all different CsPbX3
films. These layered films maintained their composition
without showing any signs of halide ion exchange even after
storing them under ambient conditions for 30 days (see Figure
S4 in the Supporting Information).
We also performed cross-sectional image analysis of PbSO4−
oleate-capped CsPbBr3 and CsPbBr3/CsPbI3 films deposited
on TiO2 (Figure 4C and D). We intentionally prepared thicker
films for this experiment, compared to the films used for
optical measurements, in order to map the composition of the
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layered films and check whether any halide ion exchange
occurred between the films following the deposition (see
Figure 4E and F). The composition analysis for the layered
film shows an iodide-rich region in the top layer and bromide
region in the bottom layer. There is a small gradient of
composition (∼100 nm) at the interface between the two
layers. This probably arises from the inhomogeneous
distribution of nanocrystals at the interface. It is expected
that the CsPbI3 nanocrystals (top layer) penetrate the voids on
the surface of the CsPbBr3 (bottom) layer, creating an
intermixed layer at the junction. As will be seen in the
subsequent discussion with emission and transient absorption
measurements, the nanocrystals deposited in these two layers
behave independently and do not exhibit any noticeable halide
ion exchange.
We also performed transient absorption measurements to
see how the excited state of layered architectures behaves
under bandgap excitation. The excited state behavior of
individual CsPbBr3 and CsPbI3 nanocrystals (capped and
uncapped) suspended in hexane was discussed in our earlier
study.20 We noted that the capping of PbSO4−oleate had no
major influence on the emission properties. A small increase in
excited state lifetime, which was observed for CsPbX3
nanocrystals following PbSO4−oleate capping, reflected
passivation of surface defects. In the present study we probed
the excited state behavior of a PbSO4−oleate-capped CsPbBr3/
CsPbI3 layered film by subjecting it to 387 nm laser pulse
excitation. The transient absorption spectra recorded at
different times are presented in Figure 5A.
The difference absorption spectrum recorded immediately
after the laser pulse excitation shows two bleach maxima at 530
and 650 nm corresponding to the excitonic peaks of CsPbBr3
and CsPbI3 nanocrystals (Figure 5A). The appearance of the
two separate bleach bands confirms that the excited state of the
two perovskites (viz., CsPbBr3 and CsPbI3) in the bilayer film
appear simultaneously following 387 nm laser pulse excitation.
(The relative magnitude of bleaching of the two bands is
determined by the extent of absorption by the individual film
and their extinction coefficient.) We have also recorded the
transient absorption spectra of individual PbSO4−oleate-
capped CsPbBr3 and CsPbI3 films, and they are presented in
the Supporting Information (Figure S5). The bleaching
recovery reflects charge carrier recombination, the major
fraction of which is completed within 1.6 ns. The absorption−
time profiles of the bleaching recovery at 530 and 650 nm are
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compared with those of individual CsPbBr3 and CsPbI3 films We also investigated the emission lifetimes of these films by
in Figure 5B and C respectively. monitoring at the emission maximum of CsPbBr3 (520 nm)
The bleaching recoveries at 530 and 650 nm were analyzed and CsPbI3 (675 nm). The emission decay of the traces
using biexponential kinetics, and average lifetimes were presented in Figure 6C and D was analyzed using
obtained for comparison (Table 1). The recovery lifetimes biexponential decay kinetics. The kinetic parameters are
compared in Table S2 in the Supporting Information. The
Table 1. Kinetic Analysis of the Bleaching Recoverya average lifetimes of CsPbBr3 and CsPbI3 films were 9.9 and
A1 τ1 A2 τav
13.4 ns, respectively, which is faster than those observed in
sample (%) (ps) (%) τ2 (ps) (ps)b solutions.20 The excited state interaction with the TiO2
A. 530 nm bleaching recovery corresponding to CsPbBr3 absorption band substrate is likely to decrease the excited state lifetime of the
CsPbBr3 film 56 62.1 44 1089.3 514.1 CsPbX3 nanocrystal film. The dependence of excited state
CsPbBr3/CsPbI3 layered film 68 50.1 32 918.7 328.1 lifetime on the electrochemical charging of TiO2 has been
B. 650 nm bleaching recovery corresponding to CsPbI3 absorption band discussed in our previous study.41
CsPbI3 film 72 76.5 28 1021.8 341.2 In the bilayer film we see emission arising from both these
CsPbBr3/CsPbI3 layered film 61 44.8 39 348.3 163.2 nanocrystals. The emission lifetimes monitored at 675 nm
a
Analysis of traces in Figure 5B and C. bτav = ∑aiτi/∑ai. (CsPbI3 emission) of the bilayer film exhibit a lifetime (14.6
ns) similar to that of single-layer (13.4 ns) CsPbI3 emission.
were slightly lower for layered films as compared to single-layer However, the emission measured at 520 nm (CsPbBr3
films. The decrease in excited state lifetime reflects excited emission) shows a slightly faster decay 3.7 ns) as compared
state interaction between the two layers. to pristine CsPbBr3 films (9.9 ns), indicating excited state
Emission Properties. The linear arrays of CsPbX3 interaction between CsPbBr3 and CsPbI3 nanocrystallites at
nanocrystals on the TiO2 film are quite emissive and inherit the interface of the CsPbBr3/CsPbI3 film. These results are
the properties of original nanocrystals specific to the identity of consistent with the lower excited state lifetimes noted in the
the halide ion. Figure 6A shows representative examples of transient absorption experiments. As indicated earlier, the
electrodeposited films under room light and UV irradiation. higher bandgap of CsPbBr3 favors the electron and hole
The emission spectra (Figure 6B) exhibit maxima at 520 for transfer to CsPbI3. Additional measurements are underway to
CsPbBr3 and at 675 nm for CsPbI3, respectively, capped with elucidate the interaction between two different CsPbX3
PbSO4−oleate. The sequentially deposited bilayer film shows nanocrystals.
the emission peaks corresponding to both CsPbBr3 and Tunable Emission Including White Phosphor. The
CsPbI3. Since CsPbBr3 nanocrystals are more fluorescent than composition-dependent bandgap tuning makes metal halide
CsPbI3, we see an enhanced emission peak corresponding to perovskites attractive for achieving emission at a desired
the former. wavelength. Mixed halide perovskites with varying composi-

Figure 6. (A) Photograph of three films under room light (top) and under UV-illumination (bottom). (B) Emission spectra of the three films: (a)
CsPbBr3 (b) CsPbI3, and (c) layered films of CsPbBr3 and PbI3. Excitation wavelength was 370 nm. Emission decay of these films monitored at
(C) 520 nm for CsPbBr3 and bilayer film and (D) 675 nm for CsPbI3 and bilayer film. (Excitation wavelength was 370 nm.)

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Figure 7. Emission spectra of PbSO4−oleate-capped CsPbCl3, CsPbBr3, and CsPbI3 nanocrystal suspensions in hexane (A) as individual
suspensions and (B) a mixture of these three nanocrystals to produce white emission. Photographs of suspensions and corresponding films under
UV light are shown as insets.
tions of chloride:bromide and bromide:iodide can allow one to
tune the bandgap in the visible range.42−45 However, there is a
problem with as-synthesized CsPbX3 nanocrystallites. One
cannot simply mix two or more pristine CsPbX3 nanocrystals
to achieve a combination of emission color since the two
different nanocrystallites undergo halide ion exchange to
produce mixed halide perovskite nanocrystals.20 However, it is
possible to suppress the halide ion exchange between different
CsPbX3 nanocrystals with PbSO4−oleate capping. We have
used this strategy to cap pristine as well as mixed halide
perovskite nanocrystals with PbSO4−oleate. The varying
composition allows us to tune the emission of the entire
visible spectrum, and the combination of two or more of these
suspensions can yield additional emissive colors. Examples of
such color combinations are shown in Figure S6 in the
Supporting Information.
We have now further explored this feature to obtain white
phosphor perovskites by mixing PbSO4−oleate-capped blue
(CsPbCl3), green (CsPbBr3), and red (CsPbI3) nanocrystal
suspensions. Figure 7A shows the emission spectra of three
separate suspensions of CsPbCl3, CsPbBr3, and CsPbI3
nanocrystals. As expected, they exhibit characteristic red (R),
green (G), and blue (B) emission as a marker for the RGB
display. Figure 7B shows the emission spectra of the three
nanocrystals when mixed together in a solution. Since the
quantum yield of each of these solutions varies from 0.02 to
0.73 (see Table S1), one needs to adjust the concentration of
each of these three nanocrystals to obtain the desired white
emission. (The absorbance spectrum of this mixed nanocrystal
suspension is shown in Figure S7.) The original RGB emission
features of the solution are well maintained, thus confirming
the retention of the individual identity of the nanocrystallites.
We have also made an effort to fill the spectral void in the
emission by introducing other PbSO4−oleate-capped mixed
halide perovskite nanocrystals with intermediate emission. The
resultant emission spectrum is shown in the Supporting
Information, Figure S8. The ability to maintain relatively high
emission shows that most of the emission is retained despite
the possibility of interparticle interactions in the excited state.
We also attempted to deposit these premixed suspensions of
three halide nanocrystals as films using electrophoretic
deposition. Indeed, we obtain white light emission from the
films similar to the one obtained in solution. The photographs
shown in Figure 7A and B confirm the ability of these films to
display emission of desired wavelength without exhibiting
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significant distortion. Efforts are underway to tap into the
tunable emission properties of PbSO4−oleate-capped CsPbX3
nanocrystals for designing LEDs. We prepared LED devices
using the procedure described elsewhere.46 The early attempts
to create green and white light emitting LEDs shown in
Figures S9 and S10 (Supporting Information) confirm the
ability of these films to produce tunable emission. The ability
to layer the PbSO4−oleate-capped CsPbX3 nanocrystals on
electrode surfaces now opens a new chapter in designing light-
emitting devices and tandem layers for solar cell applications.
These interesting properties are further aided by their ability to
retain linear alignment in electrodeposited films.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.8b04803.
Experimental methods, including nanocrystal prepara-
tion, and spectroscopic measurements (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*pkamat@nd.edu
ORCID
Vikash Kumar Ravi: 0000-0002-1708-1711
Prashant V. Kamat: 0000-0002-2465-6819
Present Address
#
Department of Chemistry, Indian Institute of Science
Education and Research (IISER), Pune, 411008, India.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Prof. Angshuman Nag of IISER, Pune, for helpful
discussions. V.K.R. acknowledges the Department of Science
and Technology (DST), Govt. of India, and Indo-U.S. Science
and Technology Forum (IUSSTF) for the Bhaskara Advanced
Solar Energy (BASE) internship and IISER Pune for a graduate
research fellowship. R.A.S. acknowledges the support of King
Abdullah University of Science and Technology (KAUST)
through Award OCRF-2014-CRG3-2268. P.V.K. and J.D.B.
acknowledge the support of the Division of Chemical Sciences,
Geosciences, and Biosciences, Office of Basic Energy Sciences
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Journal of the American Chemical Society Article

of the U.S. Department of Energy, through award DE-FC02- (30) Xiao, Z. G.; Zhao, L. F.; Tran, N. L.; Lin, Y.; Silver, S. H.;
04ER15533. This is contribution number NDRL No. 5216 Kerner, R. A.; Yao, N.; Kahn, A.; Scholes, G. D.; Rand, B. P. Nano
from the Notre Dame Radiation Laboratory. Lett. 2017, 17, 6863.

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(31) Beal, R. E.; Slotcavage, D. J.; Leijtens, T.; Bowring, A. R.;
Belisle, R. A.; Nguyen, W. H.; Burkhard, G. F.; Hoke, E. T.; McGehee,
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8894 DOI: 10.1021/jacs.8b04803

J. Am. Chem. Soc. 2018, 140, 8887−8894