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Unraveling the antisolvent dripping delay effect

Cite this: Phys. Chem. Chem. Phys.,
2020, 22, 26592
on the Stranski–Krastanov growth of
CH3NH3PbBr3 thin films: a facile route for
preparing a textured morphology with improved
optoelectronic properties†
Jitendra Kumar, ‡a Ramesh Kumar, ‡a Kyle Frohna, b
Dhanashree Moghe,c
Samuel D. Stranks b and Monojit Bag *a

Received 19th October 2020,
Accepted 3rd November 2020
DOI: 10.1039/d0cp05467d
rsc.li/pccp
Inorganic–organic hybrid perovskite materials have been a topic of interest for the last few years due to
their superior optoelectronic properties. However, the optical properties of perovskite materials are
strongly dependent on the film morphology. A textured film morphology is expected to have higher light
absorption as well as light out-coupling efficiency compared to a smooth film. There have been
numerous methods for controlling and optimizing the film morphology to achieve high efficiency in
solar cells and light emitting diodes. Here we have demonstrated that controlled anti-solvent treatment
at low temperature can lead to Stranski–Krastanov growth in CH3NH3PbBr3 thin films with superior
optical and electronic properties for light emitting diode applications. We have studied their photo-
luminescence properties at the micro- to nano-scale via fluorescence microscopy, hyper-spectral
imaging and scanning near-field optical microscopy. We have demonstrated that the nanostructured
micro-islands are highly emissive because of large quasi-Fermi level splitting (QFLS) due to the localization
of free charges in the smaller crystals. We have shown that the photoluminescence as well as electro-
luminescence can be improved by at least seven-fold due to the presence of micro-islands on a smooth
background film enhancing light out-coupling. Photo-induced photoluminescence enhancement is also
observed in smooth films while micro-islands show photo-degradation.

Introduction applications. However, perovskite grains show heterogeneity in

Halide based perovskite light emitting diodes (PeLEDs) have
become the most efficient and fastest-improving LED technology
to date, as external quantum efficiencies (EQE) of perovskite-
based light-emitting diodes have exceeded 20% in just a few
years of research.1–3 The main reason behind the success of
perovskite-based LEDs is that the thin films of these materials
can have high defect tolerance,4–6 large carrier diffusion
lengths,7–10 high photoluminescence quantum yield,11,12 ambi-
polar charge transport,13–17 wide-range emission tunability,18–20
and high colour purity.19 These properties make the perovskite
LEDs promising candidates for display and solid-state lighting
a
Advanced Research in Electrochemical Impedance Spectroscopy, Indian Institute of
Technology Roorkee, Roorkee 247667, India. E-mail: mbagfph@iitr.ac.in
b
Cavendish Laboratory University of Cambridge, Cambridge, CB3 0HE, UK
c
Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076,
India
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d0cp05467d
‡ These authors contributed equally.
their optoelectronic properties regardless of their synthesis
process;21,22 there is heterogeneity in their optical properties
even in thermally deposited films.23 Most of the studies have
discovered that the PL heterogeneity is indicative of variations in
the local density of non-radiative decay channels. Smaller grains
increase the radiative recombination fraction due to increased
carrier concentration while in larger crystals the carriers may
diffuse further due to the large diffusion length. Therefore, the
bimolecular radiative recombination fraction decreases in large
crystals.23 The presence of non-radiative pathways in perovskite
nanocrystals strongly depends on the processing conditions as
well as the film morphology. Apart from the high PL quantum
yield, high light out-coupling is another parameter to achieve
high efficiency in perovskite LEDs; therefore a textured morpho-
logy is preferable over a smooth film.24 Recently Qin et al. had
also demonstrated that a mixed crystal size can be better than a
uniform smooth film.25 Methods used for the controlled crystal-
lization of perovskite materials reported by various research
groups include gas-assisted crystallization (GAC),26–28 using

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different co-solvents to retard the rapid reaction between per-
ovskite precursors,29,30 substrate pre-heating31 and anti-solvent
treatment.29,30,32–37 Anti-solvent treatment has been proved to be
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a very efficient method for controlling the growth of perovskite
crystals. In this article we have demonstrated that the controlled
anti-solvent treatment can result in either a Frank–van der
Merwe-like (layer-by-layer) growth or a Stranski–Krastanov
(layer-plus-island) growth in methylammonium lead tri-
bromide (CH3NH3PbBr3) thin films. Textured perovskite films
show homogeneously scattered micro-meter sized island struc-
tures consisting of 20–40 nm CH3NH3PbBr3 crystals; these
micrometre sized areas are referred to as micro-islands (MIs).
Steady state or time-resolved PL measurements of these MIs
reveal the overall PL enhancement due to increased PL lifetime.
However, to understand the origin of low or heterogeneous PL
in these perovskite thin films, we need to investigate the PL at
various length-scales. There are various techniques including
super-resolution micro-spectroscopy,38,39 fluorescence micro-
scopy,23,40 hyper-spectral imaging22,23,40 and scanning near-field
optical microscopy (SNOM)41 to study PL heterogeneity at the
micro- to nano-scales. These types of microstructures are also
known to have better light out-coupling efficiency in PeLEDs.
We studied these MIs using fluorescence microscopy, hyper-
spectral imaging and SNOM to investigate the origin of high
PL in micro-islands and PL quenching in smooth perovskite
thin films.
Results and discussion
Morphology optimization
Perovskite thin film morphology can be well understood by
studying nucleation and growth mechanisms.42,43 In this work,
we have used anti-solvent treatment to prepare CH3NH3PbBr3
perovskite thin films as shown in Fig. 1a. Depending on the
adsorption thermodynamics and the kinetics of crystal growth
the prepared film can take any of three forms namely
(i) Volmer–Weber (island), (ii) Frank–van der Merwe (layer by
layer) and (iii) Stranski–Krastanov (layer plus island) (see
Fig. 1b–d).44 The film prepared without any anti-solvent treat-
ment results in the formation of large cube-like crystals with
less than 50% film coverage; we will refer to this film as the
controlled film. Slow drying of the precursor solvent during
spin coating leads to heterogeneous nucleation followed by
slow Volmer–Weber (VW) growth (Fig. 1b) which can give a
large cube like structure due to strong adatom–adatom inter-
action with the nucleation sites compared to the weak inter-
action between the adatom–substrate surfaces. Frank–van der
Merwe (FM) growth has opposite characteristics to those of VW
growth where adatom–adatom interaction is weaker than
adatom–substrate interaction leading to more uniform and
homogeneous nucleation. To prepare uniform films homoge-
neous nucleation is necessary; this can also be achieved by fast
nucleation followed by a slow growth process.31 One of the
common approaches to achieve fast nucleation is anti-solvent
treatment.42 In this case anti-solvents are non-polar (or less
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polar than the precursor solvent), miscible with the solvent
but immiscible with the perovskite precursor. Addition of anti-
solvent during spin coating can result in supersaturation and
therefore fast nucleation is achieved. This can trigger homo-
geneous nucleation leading to the formation of smooth uni-
form films. We have optimized the perovskite morphology by
controlling the delay time for anti-solvent treatment as shown
in Fig. 2. It should be noted that there are two types of film
formation during anti-solvent treatment: (i) Frank–van der
Merwe (layer-by-layer) and (ii) Stranski–Krastanov (layer-plus-
island) depending on the anti-solvent dripping delay time.
Stranski–Krastanov (SK) growth is normally seen in epitaxially
grown films on a smooth surface. SK growth can also be
realized as the intermediate growth model of a 2-dimensional
layer (Frank–van der Merwe) followed by 3-dimensional island
(Volmer–Weber) formation. There have been several theoretical
as well as experimental studies to understand SK growth in
inorganic thin films.45,46 Song et al. has also shown that SK
growth is present at the initial stage of moisture condensation47
but SK growth in solution processed perovskite thin films is
sparse.48 The general belief is that the two competing factors,
energy and entropy play a crucial role in SK growth. Therefore,
controlling the anti-solvent dripping delay time can control the
entropy, and an energetically unstable film leads to the formation
of a 3-D island from a 2-D layer. It is shown in Fig. 2e that the
formation of micro-islands (MIs) can be realized if we drip the
anti-solvent at the 30th–40th second from the start of spin coating
(3000 rpm for 80 seconds). If the dripping delay time is from the
10th to the20th s the film becomes more uniform and smooth.
However, if the anti-solvent dripping delay is more than 50th
second from the start of the spin coating, these MIs start to
disappear again. A better understanding of crystallization based
on time varied anti-solvent treatment in our case can be under-
stood in terms of change in the chemical potential of the
nucleation site (mns) as spin coating proceeds. VW growth is
characterized by the negative slope of mns which indicates strong
adatom–adatom interaction, whereas positive differential of m
implies strong adatom–surface interaction, and it is responsible
for FM growth mode as shown in Fig. 3a. Therefore, SK growth
can be seen as a positive derivative of the m–n curve followed by a
negative differential of m afterward. Variation of Gibbs free energy
predicts a critical radius, which has to be reached before crystal-
lization can start (Fig. 3c).43 Variation of Gibbs free energy can be
given as43
4
DG ¼ DGs þ DGv ¼ 4pr2 g þ pr3 DGv (1)
3
where r is the radius of the simulated spherical particles (nucleus)
and g is the interfacial energy or surface energy between the
supersaturated solution and crystalline surface and DGv is the
bulk free energy per unit volume. Maximization of Gibbs free
energy can be seen as a point of phase transition from liquid to
crystal and corresponds to equalization of the chemical potentials
of the liquid and nucleation sites. In Fig. 3a n0 represents the
critical number of particles to be added to nucleation site in order
to form a stable nucleus. Once the nucleus becomes stable the
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Fig. 1 (a) Scheme for preparation of perovskite film with controlled morphology. Scale bar in the SEM image of anti-solvent treated and without
anti-solvent treated film is given in the inset of Fig. 2, (b) schematic of Volmer–Weber (island formation), (c) schematic of Frank–van der Merwe (layer-by-
layer) and (d) schematic of Stranski–Krastanov (layer-plus-island) growth.
volume term in Gibbs free energy dominates and lowers the Gibbs
free energy of the nucleation site, therefore resulting in a negative
slope in the m–n graph (Fig. 3d), since a negative slope in m–n is
responsible for VW growth, and this explains the formation of
scattered micrometre sized crystals with less than 50% coverage in
controlled films. This indicates that the natural tendency in spin
coating is to proceed through VW growth unless the variation in
mns is controlled by an external trigger such as by controlling the
pressure, temperature or the solution concentration. Fig. 3d
shows the variation of the chemical potential as spin coating
proceeds. In our case we have chosen 80 seconds of spinning
program (3000 rpm), If we assume that the critical radius is
reached at around the 20–25th second (the film colour changes)
we can explain the observed morphologies, as anti-solvent drip-
ping can increase the chemical potential of the system by effec-
tively increasing the concentration of the solution by extracting
the excess solvent. If we drip the anti-solvent at the 10th second
after spinning starts, since the Gibbs free energy has not reached
its maximum, part of the increase in Gibbs free energy by
anti-solvent treatment is utilized to increase G to its maximum
and therefore the effective positive change in m is small in this
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case (which corresponds to FM growth which is very weak for this
film). After a few seconds of antisolvent treatment the concen-
tration of the solvent stabilizes and crystallization occurs through
VW growth and we obtain the full coverage film but with slightly
higher roughness and bigger crystal size with respect to other
antisolvent treated films (Fig. 2b and 4a). If anti-solvent treatment
is done at the 20th second which is very close to crystallization
point, a very high slope in the m–n graph results in a much more
effective FM growth and even after a few seconds when concen-
tration stabilizes the chemical potential of nucleation site remains
high compared to the substrate chemical potential for a few
seconds and crystallization keeps proceeding through FM growth
and spends a much longer time in the FM growth mode,
and therefore results in the formation of the smoothest film
(Fig. 2c and 4b). However, if anti-solvent treatment is performed
at the 30th or 40th second of spinning, the change in concen-
tration forces the crystallization to the FM mode for a few seconds
(until the concentration of solvent stabilizes) but it returns to
VW mode faster compared to films treated at the 20th second.
Therefore crystallization proceeds through a combination of FM
and VW growth modes which is the SK mode and consequently
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Fig. 2 Optimization of perovskite film for improved light out-coupling and high extraction efficiency design by spin coating. FESEM image of (a)
controlled film showing the presence of B10 mm sized micro-cubes with a partial film coverage (b–f) perovskite films obtained by anti-solvent treatment
using chlorobenzene as an anti-solvent and benzylamine as an additive to the chlorobenzene. Anti-solvent treatment of these films was performed by
optimizing the delay time for the treatment in an 80 second spinning program. Films shown in (b–f) are treated at 10, 20, 30, 40 and 50 seconds after the
start of spinning respectively.

we achieve formation of islands in the case of anti-solvent
treatment at 30–40 seconds (Fig. 2d, e and 4c, d). If we wait for
up to 50 seconds for anti-solvent treatment since crystallization
has occurred through the VW mode from 20 to 50 seconds, this
time we don’t have a flat substrate to form a smooth film, but as
soon as we add the anti-solvent the growth mode changes from
VW mode to FM mode and we achieve a full coverage film.
However, when it comes back to the VW mode, there is not much
of time left for the film to proceed through the VW mode and
form islands. The rms roughness of films prepared at 30 seconds
of delay time and 50 seconds of delay time are almost the same
but morphologies of the two films are different which indicates
that the film treated at the 30 second delay time spends more time
in the VW mode after antisolvent treatment whereas film treated
at 50 seconds of delay time spends more time in the VW mode
before antisolvent treatment. Therefore, we conclude that the
smoothest films in anti-solvent treatment can be achieved if we
drip the anti-solvent exactly at the point of formation of a stable
nucleus. And we can design micro-islands if we drip the anti-
solvent at a suitable time when both FM and VW growth modes
contribute equally resulting in a SK growth. The rms roughness of
these films is shown in Fig. 4f. For more quantitative analysis
further experiment/simulation/modelling is needed to understand
SK growth in perovskite thin films. In this study we call these SK
growth films as textured films because these films show the
formation of micrometre-sized islands. These islands comprise
of smaller particle size (B20–40 nm) distributions (Fig. S1, ESI†)
compared to a relatively larger grain size (B300 nm) in the
background. The XRD pattern index matches well with cubic
MAPbBr3 for both the controlled and anti-solvent treated films
(Fig. S2, ESI†). Using scanning electron microscopy (SEM) and atomic
force microscopy (AFM) image analyses of MIs, the average height of
MIs is found to be B120 nm and an average distance between two
such micro-islands is around 3 mm (Fig. S4, ESI†), a 25  25 mm2 area
was scanned with the help of AFM setup for this measurement. The
scan area is large enough to include a number of micro-islands in
order to calculate the average height of these micro-islands.
Photoluminescence measurements
Fluorescence imaging
The controlled film shows very weak PL intensity and so does
the smooth perovskite film prepared by antisolvent treatment
after a 10th–20th second delay. This could be due to high PL
quenching at the defect sites or at the hole transporting layer.
The PL intensity was found to be maximum for the textured
film prepared at the 40th second delay amongst all the film
types, though it was spatially inhomogeneous because of the
presence of MIs. Films prepared with the 30th second and 50th

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Fig. 3 Schematic diagram of controlling chemical potential with the help of anti-solvent treatment during crystallization of perovskite films. (a) Change
in the chemical potential as a function of adsorbed particles/molecules, (b) change in the chemical potential from the liquid phase to the crystalline
phase, (c) variation of Gibbs free energy as a function of particle radius, and (d) proposed variation of the chemical potential during the antisolvent
dripping. The dotted lines represent the chemical energy variation without anti-solvent dripping while solid lines represent the chemical energy variation
at different antisolvent dripping delay times.

second delay show a moderate PL intensity (Fig. S5, ESI†). The
areas of the textured film that are away from the MIs are similar
to those of the smooth film. Therefore, our main focus is to
understand the spatially heterogeneous PL emission of the
textured film. A high PL intensity is the signature of low defect
density and purity of the material. In fluorescence microscopy,
we have observed that the PL intensity at MIs is much higher
than that of the regions away from the islands (Fig. 5a); this
could be obvious because of the anti-correlation of PL intensity
and grain size.49 Fig. 5b is the overlay image of transmis-
sion and fluorescence mode images which indicates that the
brighter regions are MIs. We speculate that the presence of MIs
can improve the light out-coupling efficiency by providing the
convex–concave geometry at the perovskite air interface, and
thus it could help to improve the PL emission by at least 7-fold
in our case. SEM and AFM images of these MIs show the
formation of a textured surface which can improve the light
out-coupling efficiency.50 In Fig. 5c we show the histogram of
PL intensity (arbitrary unit) to compare the contribution of dark
and bright regions. Fig. S6 (ESI†) depicts the PL intensity
counts; o90 grayscale value (GSV) are from the regions which
are away from the MIs whereas 100 GSV mark the boundary
of the MIs. Therefore, we have divided the histogram into
three different regions; the low-intensity region shows the PL
intensity clustered around 20 GSV whereas high-intensity end
shows a peak around 140 GSV. This indicates that the MIs
can increase the PL intensity by at least 7 times compared to the
smooth films (the non-island site is itself a smooth film).
The inset of Fig. 5c is the magnification of the y-axis for the
high-intensity region. Fig. 5d shows a good linear correlation

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Fig. 4 Perovskite film morphology optimization by controlling antisolvent treatment delay time (a)–(e) show AFM images of perovskite films treated at
10, 20, 30, 40 and 50 second delayed treatment respectively. (f) Shows variation of rms film roughness vs. anti-solvent treatment delay. The
measurements were carried out on multiple substrates and at multiple areas to confirm the reproducibility.
coefficient (R = 0.72) between the PL intensity and the area of
MIs. Although the high-intensity regions are associated with
the larger MIs, this relation seems to saturate around a charac-
teristic micro-island of area 1.8 mm2. Next, we performed the
steady-state PL measurements for all the samples (Fig. S5,
ESI†), by taking the ratio of integrated PL intensity We observed
that the PL intensity from textured films shows an B10-fold
increase from controlled film PL intensity and B7.5-fold
increase from smooth films, which is consistent with the
observations from fluorescence microscopy. With the help of
AFM image analysis and cross-sectional FESEM images (Fig. S4,
ESI†) we found that the local volume fraction increased at MI
sites is only B32% whereas overall volume fraction increase is
B6.8%. This analysis indicates that the 750% increase in PL is
not just the consequence of higher effective film thickness but
it could be the result of high PL quantum yield due to the
smaller crystal size,51 improved photon absorption by light
trapping as well as PL out-coupling due to MI sites. Recently,
we have also shown that this type of textured morphology forms
a better perovskite/HTL interface in n–i–p structured PLEDs.52
We believe that the inhomogeneity in the widefield PL mapping
is mainly because of the charge carrier confinement as well as
trap distribution since the contribution of diffusion-limited
decay pathways is weak for widefield illumination.
Hyper-spectral PL imaging
To investigate the detailed photoluminescence properties of
these MIs we have carried out hyperspectral PL imaging on
these MIs as well as the smooth background film. The PL
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mapping by hyperspectral imaging is still diffraction limited;
therefore, the limitation due to grain boundaries could not be
resolved in the smooth film. To find out the mechanism of non-
radiative recombination losses in smooth perovskite films,
scanning near field optical microscopy (SNOM) is introduced
to investigate such lateral PL intensity variations. From hyper-
spectral PL microscopy, we can see that there are regions of the
textured film at which the PL spectrum is more skewed; these
are the areas of low PL intensity. The shape of the spectrum is
fitted with a bi-Gaussian function (Fig. 6 and Fig. S7, ESI†).
We attribute these two Gaussians as a result of two different
emitters; the presence of two emitters could be related to the
different size of the crystals. Some of the high energy photon
can be reabsorbed at low energy sites. Thus, the PL intensity
depends on how efficiently the charge carriers can diffuse
toward the quencher sites and also on the quenching effi-
ciency of the quencher. PL inhomogeneity in the micro-cube
for the controlled film can be found in the ESI† (Fig. S8).
To investigate further, we have estimated quasi-Fermi level
splitting (QFLS) for the micro-island site as well as for the
background film (Fig. S9, ESI†). QFLS is a characteristic of
purity of the material and is normally indicative of the maxi-
mum achievable open-circuit voltage in perovskite solar
cells.53,54 Here we have calculated QFLS for the brightest,
moderately bright and the least bright location of the film
using generalized Planck’s law.55
 
YPL ðE Þ Dj E
ln 23 2
¼  (2)
10 E kT kT
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Fig. 5 (a) PL map of perovskite films taken using a widefield fluorescence optical microscope showing scattered emission (area scanned 100 
100 mm2), (b) overlay of transmission and fluorescence images indicating that the PL signal is mainly coming from few micrometre-sized areas; in the SEM
image these areas are identified as micro-islands, (c) is the histogram of PL intensity, the histogram is divided into three parts orange shaded region (low
intensity) is the region which is far away from micro-islands, blue shaded region is the boundary of the plane and micro-islands sites of the perovskite
film, violet region (high-intensity region) represents the emission from micro-islands, which is again shown in the inset just to magnify the y-axis,
(d) scatter plot of PL intensity vs area of the micro-island showing a good linear correlation (R = 0.72). (e–g) Heterogeneity at different scales in perovskite
films (e) PL map taken using a fluorescence microscope (f) PL map of perovskite film around one of the micro-islands taken by hyperspectral PL imaging
(g) fluorescence mode image of smooth background film taken by SNOM.

where YPL(E) is the absolute magnitude of the photon flux
detected outside the sample, Dj is the QFLS, E is the photon
energy, k is the Boltzmann constant and T is the sample
temperature. These values of calculated QFLS are tabulated
in Tables S1 and S2 (ESI†). It is to be noted that if YPL(E) is not
calibrated absolute QFLS may not be accurate. In this context
we will focus only on the relative changes rather than the
absolute value of QFLS. To cross-examine our results for
reliability we have plotted ln(YPL(E)/1023E2) versus ho/kT
and found that the slope is close to unity (Fig. S10, ESI†).
It is interesting to see that the value of the QFLS at a least-
bright point is 72 meV lower than the value of QFLS at the
brightest point; this indicates that the dark areas have higher
trap-limited non-radiative recombination. This could be
because of efficient hole extraction from smooth films resulting
in strong PL quenching and weaker hole extraction from micro-
islands giving rise to a weaker PL quenching which can be one
of the reasons for heterogeneous PL emission across the film.
Since the distance between the brightest and the least bright
points are within the charge carrier diffusion lengths in per-
ovskites, we can say that the difference in PL intensity levels is
most likely trap limited rather than diffusion limited which is
consistent with the results published by DeQuilettes et al.22
Then we calculated the ratio of the integrated PL intensity
from micro-island sites (1) and non-island sites (4) and found
that the PL ratio is consistent with the widefield PL imaging
and steady-state PL measurements; thus hyperspectral PL
measurements also strengthen our speculation of improved
light out-coupling because of MIs.
SNOM imaging
In our study of perovskite films, the grain size was close to the
diffraction limit and created difficulty for widefield or hyper-
spectral PL imaging to probe the sub-grain heterogeneity.
To probe the diffraction-limited region we performed SNOM
having a resolution less than 100 nm (pixel size 50 nm), Fig. 7
shows a PL intensity map taken by SNOM. Surprisingly we
found that although the expected resolution of SNOM was
lower than the grain size, we did not observe a PL contrast at
the length scales of grain size due to larger diffusion length in
perovskites. As suggested by DeQuilettes et al. we can expect
a lower PL intensity at the grain boundaries.22 In another
study by Yang et al. they have shown that in CH3NH3PbI3
perovskite films the grain boundaries do not lead to increased
recombination,49 rather non-radiative recombination may
occur at the grain interior. Although Yang et al. reported that
the grain boundaries in their study were generally dimmer, the
lifetime at the grain boundaries was not too bad compared to
the grain interior. We associate the absence of contrast at the
length scale of grain size to the fact that in near field excitation
the diffusion process may dominate over the trap limited
recombination at the grain boundaries, and thus, our results
are consistent with the findings of Yang et al. Fig. 7c shows the
PL spectra of four different tagged regions in Fig. 7a. The PL

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Fig. 6 Hyperspectral PL imaging: correlated (a) transmission and (b) PL mode images taken using a hyperspectral PL microscope (c) PL spectrum taken
from different locations of the perovskite film; figure serves to show the skewness of the PL spectrum from a different location. (d) Normalized PL
spectrum showing B16 meV distribution in the emission spectrum.
Fig. 7 Near field scanning optical microscopy: (a) SNOM PL image of the
background (smooth) film (b) 3D image of PL map (c) PL spectrum of
brightest (i), second brightest (ii), moderately bright (iii) and lowest intensity
regions (iv) tagged by green square, red circle, orange and blue triangle
respectively, (d) normalized PL spectrum showing PL broadening (low
energy tails) at different emitter sites.
peak position is same for all the spectra while the low energy
tail states from low PL regions are slightly broader compared to
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those from the high PL regions, which is an indication of
higher trap density. It indicates that the smooth funnelling
of charge carriers from low defect locations to high d
efect locations quenches the PL intensity. Therefore, the dark
regions (region iv) are quite large compared to the grain size in
perovskite thin films.
Photo-induced PL enhancement
We have also observed the overall PL enhancement (Fig. 8 and
Fig. S11, ESI†) when samples are studied under a fluorescence
microscope under ambient conditions. This is an important
aspect as far as device efficiency or stability is concerned. This
could be due to photocuring of perovskite nanocrystals in the
presence of oxygen as explained by the Scheblykin group.56
Photo-induced PL enhancement is also attributed to ion migra-
tion by many researchers.57,58 For both the controlled and
anti-solvent treated films, a PL enhancement is observed. The
enhancement of PL intensity can be attributed to two simulta-
neously occurring processes. The first is due to a decrease in
the concentration of defect sites (normally deep trap states) by
photochemical reactions with oxygen and the second process
could be due to the reduction in halide interstitial species
and halide vacancy species because of the ion migration.57,58
Under light irradiation, Pb2+ oxidizes to PbO in Pb-clusters
reducing their quenching activity. Alternatively, reactive oxygen
species could passivate halide vacancies.59 We find that the PL
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Fig. 8 Photoluminescence enhancement of anti-solvent treated film at different time snaps (at t = 0, 40, 80, 120 s). Graphical representation of PL
enhancement from the micro-islands and the background obtained from multiple pixels of the entire film; marked regions from island and non-island
site are selected and an average of their PL behaviour is shown in the graph.
enhancement is crystal geometry specific. PL enhancement in
controlled films is faster at the edges compared to the central
part of the micro-cube, which is because the high surface to
volume ratio near edges provides a larger cross-section for
oxygen diffusion from the environment to react and alter the
photophysical properties of the material. Interestingly, MIs
show an overall decrease in the PL intensity despite their higher
surface area. This could be because of high carrier density
leading to photo-induced degradation of the nanocrystals.56
However, PL enhancement is observed in smooth background
films. This could be explained as being due to the competition
between photo-induced trap reduction and photo-induced
trap generation. This type of coexistence of light induced PL
quenching and PL enhancement has been very recently
observed and explained by Haoran et al.60 They demonstrated
that higher irradiation densities (higher Voc) start to increase
the photo induced trap generation rates and may dominate the
photo induced trap reduction. QFLS is the measure of internal
voltage which is responsible for ion migration. In our case we
have observed higher QFLS at micro-island sites and relatively
low QFLS in smooth background films. Observation of photo-
activation in background films is due to annihilation of Frankel
defects,57 whereas as higher QFLS in micro-islands may create
additional halide vacancies and result in a photo darkening
effect due to increase in defect densities with time. From Fig. 8
we can see that rate of photo-brightening (trap annihilation) is
faster (tbkg = 39 s) compared to rate of photo-darkening (tisland =
109); that is why we observe an overall photo enhancement
in our samples. The presence of both photoactivation and
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photodegradation in same film again indicates the presence
of SK growth where both the stressed (non-island site) and
relaxed regions (micro-islands) are present. Photoactivation in
non-island sites is possible because of the regions formed by
FM growth mode creating more Frankel defects (interstitial
species and vacancy species), while in the micro-islands formed
by VW growth mode the stress is released and therefore these
micro-islands are both stress and defect free.61
Electrical characterization
We have fabricated perovskite light emitting diodes (PeLEDs) in
both p–i–n as well as n–i–p device structures. It has been
observed that the overall device performance is significantly
improved for the textured film as the active layer. The electro-
luminescence spectra (EL) show at least 7-fold increase in
intensity for the textured films compare to the smooth films
(see Fig. S13, ESI†). However, the overall quantum efficiency
was low due to the unoptimized device structure and also
underestimated external quantum efficiency (EQE) measurements
because of the linear photodetector used to measure output
photon flux. Further improvement in the device structure as
well as interface engineering is thus needed to achieve high
performance PeLEDs.
Conclusions
In summary, we have designed a textured morphology of
perovskite films by optimizing the delay time for anti-solvent
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Paper
treatment. Stranski–Krastanov growth kinetics at low tempera-
ture can be realized in the solution process perovskite film
deposition. Our results confirm that the presence of micro-
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islands on smooth perovskite films can improve the PL emis-
sion by at least seven-fold. We studied the perovskite samples
starting from long range to sub-grain resolution, using wide-
field microscopy, hyperspectral PL imaging, and the SNOM
technique. Widefield PL indicates that the heterogeneity in PL
emission is mainly due to charge carrier confinement as well as
trap limited recombination since the diffusion in widefield
measurements is not a limiting factor for PL intensity.
By hyperspectral imaging, we have shown that the intensity
variation in the PL spectrum for different regions of interest is
due to the presence of multiple emitters, and the distribution
of defect density. The estimated QFLS at the brighter point was
found to be 72 meV higher compared to QFLS at low-intensity
regions. This indicates that the micro-islands do have high
quantum yield, and at the same time they help to improve
the out-coupling efficiency by providing a concave–convex
geometry. Finally, with the help of SNOM, we have shown that
the intensity variation in the background film is not diffusion
limited, but rather a trap-limited process. The strategy to
minimize the bulk non-radiative sites can be the next step to
achieve more homogeneous and high PL emission. We have also
observed the photoinduced PL enhancement in perovskite micro-
cubes as well as in smooth films; we believe that this effect is a
result of photo-induced curing of defect states due to reaction with
oxygen related species and ion migration under light irradiation.
However micro-islands show overall decrease in PL intensity which
could be because of higher QFLS and the generation of additional
halide vacancies due to photo-induced ion-migration at micro-
island sites. The overall device performance is also improved when
the textured morphology is used as the active layer.
Methods
Materials
All the chemicals were used as received, including methylamine
solution (40%, Central Drug House Pvt. Ltd), HBr (48%, Sigma-
Aldrich), ethanol (Analytical CS Reagent), propan-2-ol (99.999%
AR/ACS, SDFCL), N,N-dimethylformamide (DMF, anhydrous
99.8%, Sigma-Aldrich), (dimethyl sulfoxide (DMSO) dried, SRL
Chemicals), chlorobenzene (extra pure AR, SRL chemicals),
benzylamine (99% Sigma Aldrich), poly(3,4-ethylene dioxythio-
phene)–poly(styrene sulfonate) (PEDOT:PSS conductive grade,
Sigma-Aldrich), and lead bromide (99.9 Sigma-Aldrich). MABr
was synthesized by reacting 27.8 ml of methylamine solution
(40%, Central Drug House Pvt. Ltd) with 44 ml of aqueous HBr
(48%, Sigma-Aldrich) at 0 1C with continuous stirring in
a conical flask for 4 h. The solvent was removed and the
precipitate was recovered by using rotary evaporation at
60 1C. The precipitate was then washed with diethyl ether to
obtain a white MABr powder. Finally, the white powder was
collected by filtration and dried at 60 1C in a vacuum oven for at
least 24 h before use.
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Device fabrication
ITOs were cleaned following the standard procedure which is
cleaning of ITO substrate by soap solution followed by sonica-
tion in distilled water, acetone, and IPA, respectively, for ten
minutes each. After that, these substrates were exposed to
UV–ozone cleaning for 10 minutes. PEDOT:PSS (1.3 wt% dis-
persion in H2O) was further diluted in IPA as 1 : 1 and spin-
coated on the cleaned substrates at 5000 rpm for 60 seconds
followed by annealing at 120 1C. For perovskite film coating,
a controlled humidity chamber was used for fixing the humid-
ity at 25%; spin coating was done at room temperature (25 1C).
Perovskite films were spin-coated onto PEDOT:PSS coated ITO
substrates. For perovskite coating we have followed an anti-
solvent treatment method for controlling the crystallization of
perovskite, and therefore we have used chlorobenzene as an
anti-solvent. Benzylamine was used as an additive34 for the
anti-solvent by 0.5 wt%, and 0.6 M solution of CH3NH3Br and
PbBr2 in a DMF/DMSO (7 : 3) co-solvent was used to deposit
these films. For controlled films we deposited perovskite pre-
cursor solution by spin coating at 3000 rpm for 80 seconds, and
5 seconds of acceleration time was given to achieve the maximum
speed. For the antisolvent treated textured film, 120 ml of the anti-
solvent solution was dropped at the 40th second of spinning
whereas the plane film morphology could be achieved by dripping
the anti-solvent at the 20th second of spinning. The experiment
was performed multiple times observing consistency in the results.
Finally, these films were transferred onto the hot plate maintained
at 100 1C for annealing for 15 minutes. All the optical and
structural characterizations are performed on these perovskite
films directly coated on PEDOT:PSS. For device fabrication we
spin coated 20 mg ml1, 2,2,2-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-
benzimidazole) (TPBi) solution in chlorobenzene. After spin
coating TPBi, we transferred these devices to the thermal evapo-
rator for electrode deposition, which was directly connected to a
nitrogen filled glovebox; finally 80 nm silver electrodes were
deposited at 2  106 torr at a deposition rate of 1 Å s1.
Characterizations
FESEM
The morphology and EDX of the perovskite samples were
characterized using a FE-SEM QUANTA 200 FEG Field Emission
Scanning Electron Microscope.
AFM
An INTEGRA, NT-MDT-INTEGRA instrument was used for AFM
image acquisition. Large area scanning (25  25 mm2) is used to
capture more number of micro-islands for calculation.
Optical microscope
An Evos FL inverted microscope with a 40 objective and GFP
light cube was used for capturing optical images in optical and
fluorescence modes.
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Hyperspectral microscopy
Hyperspectral images were taken using a Photon etc. IMA-VIS
system. Both the samples were measured using a 100 Nikon
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air objective and a 405 nm continuous wave laser. The spectral
measurements are performed by scanning the angle of the
grating relative to the emitted light from the sample to form
images at each wavelength which are stacked to form a data
cube. The spectral resolution is in principle guided by the
bandwidth of the holographic grating in the setup and is
B0.2 nm, although we have taken step sizes of 2 nm in this
case. For spectral measurements 0.3 and 4 seconds integration
time per wavelength was taken for anti-solvent treated and
controlled film respectively and the light intensity was kept
constant for all measurements.
SNOM-PL map acquisition
For PL image acquisition an area of 5  5 mm2 was scanned for
100 points per line and a 100 line scan was used to construct
the PL map. An integration time of 0.10495 seconds was used to
collect the PL signal. For PL mode microscopy a continuous
wave LASER of 355 nm was utilized for sample excitation,
whereas DUO420-OE 20432 CCD maintained at 59 1C was
used to collect the PL spectrum. The spectral resolution of this
setup is 0.13 nm.
X-Ray diffraction
The XRD spectrum was recorded on a Bruker D8-Advance with a
1.54 Å monochromatic radiation. The spectrum was recorded
from 51 to 551 with a step size of 0.021.
EQE
External quantum efficiency was measured using a calibrated
planner silicon photodetector directly placed on top of the LED.
Funding sources
The work is partially supported by an SERB grant, Department
of Science and Technology, INDIA under award no. ECR/2016/
001530 dated 24/03/2017.
Abbreviations
PeLEDs Perovskite light emitting diodes
SNOM Scanning near field optical microscope
MIs Micro-islands
GSV Grey scale value
ROI Region of interest
Conflicts of interest
There are no conflicts to declare.
26602 | Phys. Chem. Chem. Phys., 2020, 22, 26592--26604
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Acknowledgements
M. B. acknowledges Laura-Isabelle Dion-Bertrand from
PHOTON ETC for discussion on hyperspectral imaging. J. K.
acknowledges Hitesh Mamgain from WITec for carrying out
SNOM measurements. J. K. and R. K. acknowledge Dr Dinesh
Kabra from IIT Bombay for useful discussions. J. K. acknowl-
edges Priya Srivastava for synthesizing MABr. M. B. acknowl-
edges Department of Science and Technology, India, for partial
support to carry out this work under the award no. ECR/2016/
001530 dated 24/03/2017. K. F. acknowledges a George and
Lilian Schiff Studentship, Winton Studentship, an Engineering
and Physical Sciences Research Council (EPSRC) studentship,
Cambridge Trust Scholarship, and Robert Gardiner Scholarship.
S. D. S. acknowledges the Royal Society and Tata Group (UF150033).
S. D. S and K. F. acknowledge the EPSRC (EP/R023980/1).
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