Chemically Tailoring the Dopant Emission in Manganese-Doped CsPbCl3 Perovskite Nanocrystals

Article abstract of DOI:10.1002/anie.201703863

Doping in perovskite nanocrystals adopts different mechanistic approach in comparison to widely established doping in chalcogenide quantum dots. The fast formation of perovskites makes the dopant insertions more competitive and challenging. Introducing alkylamine hydrochloride (RNH₃Cl) as a promoting reagent, precise controlled doping of Mn^II in CsPbCl₃ perovskite nanocrystals is reported. Simply, by changing the amount of RNH₃Cl, the Mn incorporation and subsequent tuning in the excitonic as well as Mn d–d emission intensities are tailored. Investigations suggested that RNH₃Cl acted as the chlorinating source, controlled the size, and also helps in increasing the number of particles. This provided more opportunity for Mn ions to take part in reaction and occupied the appropriate lattice positions. Carrying out several reactions with varying reaction parameters, the doping conditions are optimized and the role of the promoting reagent for both doped and undoped systems are compared.

Full text of DOI:10.1002/anie.201703863

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Accepted Article
Title: Chemically Tailoring the Dopant Emission in Mn doped CsPbCl3
Perovskite Nanocrystals
Authors: Narayan Pradhan, Samrat Das Adhikari, Sumit K. Dutta,
Anirban Dutta, and Amit K. Guria
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201703863
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10.1002/anie.201703863
Angewandte Chemie International Edition
Chemically Tailoring the Dopant Emission in Mn doped CsPbCl3
Perovskite Nanocrystals
Samrat Das Adhikari, Sumit K. Dutta, Anirban Dutta, Amit K. Guria and Narayan Pradhan*
Abstract: Doping in perovskite nanocrystals adopts different
mechanistic approach in comparison to widely established doping in
chalcogenide quantum dots. The fast formation of perovskites
makes the dopnat insertions more competitive and challenging.
competitive reactiveness of the Mn precursor along with Pb is
highly required for efficient Mn insertions.[1h] At the desired
reaction temperature (180-200 oC), being the reaction is very
fast, introduction of sufficient Mn(II) precursor concentration is
required for establishing a favorable condition for inserting only a
few percentage of Mn into the host crystal.[1h] Hence, this
Introducing alkylamine hydrochloride (RNH3Cl) as
a promoting
reagent, precise controlled doping of Mn(II) in CsPbCl3 perovskite
nanocrystals is reported. Simply, by changing the amount of RNH3Cl, demands more facile approach and in-depth study of the
the Mn incorporation and subsequent tuning in the excitonic as well
as Mn d-d emission intensities are tailored. Investigations suggested
that RNH3Cl acted as the chlorinating source, controlled the size,
and also helps in increasing the number of particles. This provided
more opportunity for Mn ions to take part in reaction and occupied
the appropriate lattice positions. Carrying out several reactions with
varying reaction parameters, the doping conditions are optimized
and the role of the promoting reagent for both doped and undoped
systems are compared.
reaction chemistry for exploration of doping in perovskite
nanocrystals.
Understanding the chemical pathways of formation of
CsPbCl3, herein, the doping of Mn ions is successfully achieved
with minimal Mn(II) precursor by introducing a reaction activating
agent alkylamine hydrochloride (RNH3Cl). The intensity of the
dopant emission is tailored with the function of the amount of
added RNH3Cl. Importantly; the approach did not require the
traditional follow up fast cooling process, rather constantly
maintained at 180-200oC. Investigation suggested that RNH3Cl
helped in creating more number of particles with smaller
dimension which provided more opportunity for Mn(II) to take
part in a comparatively slow process. Contrary to similar
previous reports, here successful doping was achieved with
initial 5% Mn precursor (with respect to Pb) in the reaction,
which effectively doped ~1.3 % Mn; a breakthrough of doping in
ionic solids. The emission was also observed bright (QY ~27 %)
with minimal host excitonic emission. The effect of RNH3Cl on
synthesis of both doped and undoped systems are investigated
in relation to size tuning, percentage of dopant ions
incorporation and the tailoring of the optical emissions and are
reported in this communication.
For doping Mn(II) in CsPbCl3 nanocrystals, high
temperature synthetic protocol, typically between 180-200 oC,
was adopted. Molten RNH3Cl (mixture of oleylamine and HCl,
see experimental section in Supporting Information) was
introduced in the reaction flask along with PbCl2, MnCl2 and
other reagents. At ~180 oC, Cs-precursor was swiftly injected.
Samples were collected as a function of time and also the
amount of RNH3Cl, and analyzed. Figure 1a shows the
schematic presentation of the reaction and the formation of Mn
doped CsPbCl3 (Mn:CsPbCl3) nanocrystals. The reagent
RNH3Cl, may be obtained from HCl and several alkylamines
(octyl, dodecyl, hexadecyl etc.) though for liquid nature at room
temperature oleylamine was preferred. Under illumination, the
digital image of the reaction flask containing Mn:CsPbCl3
nanocrystals is shown in Figure 1bwhere the orange color
preliminarily reflected as their origin from Mn d-d emission. The
absorption and photoluminescence (PL) spectra of undoped
CsPbCl3 obtained in similar reaction in presence of 0.5 ml
RNH3Cl are shown in Figure 1c.PL spectra of Mn:CsPbCl3
nanocrystals normalized at the exciton emission are shown in
Figure 1d. For understanding the impact of concentration of
RNH3Cl, the distinctive PL spectra of Mn:CsPbCl3 nanocrystals
obtained with variable amount of RNH3Clat normalized OD (370
nm) are presented in Figure 1e-h. As observed, the intensity of
the excitonic blue emission slowly diminished with evolution of
intense Mn d-d emission at 585 nm. Mn and Pb precursor, and
D
oping in perovskite nanocrystals opens up a new era of
current research.[1] Beyond the widely established color tunable
bandedge emissions of halide perovskites,[2] on doping with
appropriate dopants the optical emission of these nanocrystals
might further tune to a new spectral window.[1h,3] For covalent
chalcogenide nanocrystals where the classical mechanism of
crystal growth is largely understood, doping is established as a
phenomenon of surface adsorption.[4] Here, dopants ions are
adsorbed onto the energetically favorable facets of the host
nanocrystals during growth. However, in inorganic halide
perovskite nanocrystals the fundamentals of crystal growth is
still not widely understood and typically being ionic crystals,
reaction proceeds much faster. Hence, the adsorption
mechanism which needs controlled nanocrystals growth became
difficult for perovskites doping. Another doping process adopted
for chalcogenides is via ion diffusion where dopant ions are
selectively exchanged or diffused inside the host crystal.[4e,5]
However, achieving control over precise ion exchange in dopant
level is yet to be established in perovskite nanocrystals.[4f] Hence,
doping in these nanocrystals remains challenging and needs
deeper fundamental understanding of the crystal formation and
also developments of facile synthesis procedures.
Among various transition metal dopants, doping Mn(II) ion
in chalcogenides nanocrystal hosts is largely understood.[4a,5g,6]
The uniqueness of this dopant is its long lifetime spin polarized
d-d emission in yellow-orange spectral window. For perovskite
hosts, the compatible band alignment and efficient host exciton
energy transfer to Mn states are more favorable in CsPbCl3.[1h]
As Mn (II) ions reside on Pb(II) positions in the crystal lattice, a
S. Das Adhikari,[+] S. K. Dutta,[+] A. Dutta, A. K. Guria, Dr N. Pradha
Department of Materials Science, Indian Association for the Cultivation of
Science, Jadavpur, Kolkata, India 700032.
E-mail: camnp@iacs.res.in
[+]These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the
document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201703863
Angewandte Chemie International Edition
Figure 1.(a) Schematic presentation of the synthesis of Mn doped CsPbCl3 nanocrystals using RNH3Cl as the activating reagent. Atomic model shows the
placement of Mn(II) in substitution position of Pb(II) in CsPbCl3 crystal lattice. (b) Digital image showing Mn doped CsPbCl3 nanocrystals in reaction flask under
illumination. (c) Typical UV-vis and PL spectra of CsPbCl3 nanocrystals obtained without Mn precursor. (d) Overlapped PL spectra obtained in similar reactions with
variable RNH3Cl concentration normalized at the excitonic emission. (e-h) PL spectra showing dual emissions with successive increase of amount of RNH3Cl in the
reaction mixture. MnCl2 was taken 5 mole percentages to PbCl2. For all these spectra, samples were taking after 1 min of injection of Cs precursor at 180 oC without
following the ice cooling approach. (i) Excited state decay lifetime of Mn d-d emission (Emission at 585 nm). Excitation wavelength is 370 nm.
also all other reactants were unchanged in all these reactions.
Photoluminescence excitation (PLE) spectra presented in Figure
S1 showed the bandedge for all cases remained overlapping
reflecting the Mn emission originated from the host CsPbCl3
nanocrystals. The excited state decay lifetime suggested the
long lifetime of ~1.4 ms (Figure 1i) which was typical for Mn d-d
emission. All these results suggest Mn(II) ions are doped in
CsPbCl3 perovskite nanocrystals.
Before investigating the correlation of the amount of
RNH3Cl salt taken in the reaction system with the percentage of
Mn incorporation, control reactions without the salt were
performed. Reactions with fast cooling and also retaining at 180
oC were compared. Figure 2 presents the PL spectra of series of
reactions with varying the Mn concentration (with respect to Pb)
from 2 to 100% both in presence (Figure 2a) and absence
(Figure 2b) of RNH3Cl. Interestingly, it was observed that the
intense Mn-emission with minimal exciton emission was
observed even with 5 % of Mn(II) precursor in presence of
RNH3Cl. However, under identical reaction conditions, with
increase of Mn concentration further did not improve the PL
intensity suggesting 5 % Mn might be enough for obtaining the
optimized Mn doped CsPbCl3 nanocrystals in our reaction
conditions. In contrast, without salt no Mn d-d emission
appeared with this amount of Mn(II) precursor. It has been noted
that even with 5 % Mn taken along with RNH3Cl, the relative
Figure 2. PL spectra of Mn doped CsPbCl3 nanocrystals obtained (a) in
intensity of the Mn-emission with respect to exciton emission
was superior to that of 100 % MnCl2 taken without the salt.
These observations clearly concluded that the RNH3Cl helped
presence of 0.5 ml RNH3Cl, (b) in absence of RNH3Cl keeping the reaction
at 180 oC and (c) without RNH3Clwith rapid cooling to room temperature
after Cs precursor injection. Right hand panel shows the molar percentage
significantly on the doping of Mn in CsPbCl3 nanocrystals.
Presence of Mn in all the above samples were measured
by energy dispersive spectral (EDS) analysis and only ~1-8 %
Mn (with respect to Pb) of was observed in these samples. For
of Mn with respect to Pb. Amount of Mn with respect to Pb ions is shown in
inset of (a) and (c). Representative absorption spectra for these PL spectra
are shown in Figure S2.
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10.1002/anie.201703863
Angewandte Chemie International Edition
Figure 3. (a-c) TEM images of doped CsPbCl3 nanocubes obtained from samples without and with 0.1 ml and 0.5 ml RNH3Cl taken in the reaction flask. (d)
TEM image of doped CsPbCl3 nanocubes obtained with 10 min annealing at 180 oC with 0.5 ml RNH3Cl. (e) Powder XRD patterns from the doped nanocrystals
with and without RNH3Cl and both samples collected after 1 min annealing at 180 oC. More TEM images are provided in Figure S4.
50% Mn precursors with respect to Pb, led to only 7.5 % Mn in
the purified sample (Figure S3); but the best emission with 5%
Mn could replace only 1.3 % Pb to Mn in the crystal lattice
(inset, Figure 2). Point EDS on transmission electron
microscope (TEM) was chosen as the appropriate tool as it was
associated with small area.
While above spectra were obtained from the samples
collected at 180oC from the reaction, samples collected from
room temperature after rapid cooling following traditional
approach were also measured for comparison. Figure 2c shows
the PL spectra obtained with varying MnCl2 concentration and
ice cooling the flask after Cs-oleate injection without the
activating chloride reagent, RNH3Cl. Unfortunately, no significant
difference in the evolution of Mn d-d emission was observed
even with 5 % or more MnCl2 concentration. This clearly
suggested that RNH3Cl became the promoting reagent which
helped efficient doping at elevated reaction temperature and
with minimum Mn precursor concentration.
solution. Powder X-ray diffraction (XRD) patterns for these
samples are shown in Figure 3e and the obtained peak position
resembled with cubic phase of CsPbCl3 (JCPDF: 84-0438). The
FWHM of the peaks suggested that the larger size particles for
the nanocrystals obtained in absence of RNH3Cl and this
resembled with obtained TEM images. These results further
concluded that the fast cooling might not be required for
obtaining either doped or undoped CsPbCl3 nanocrystals.
All the above results obtained in presence of RNH3Cl
corroborated that the chlorinating agent could control the size
and also stabilize the nanocrystals at higher temperature. It
could be further stated that number of nanocubes increased with
decrease of their size as a function of increase in the amount of
RNH3Cl. This is assumed considering Cs precursor is the
limiting reagent and reacts completely during the nanocrystals
formation. Hence, RNH3Cl only controlled the density of
formation of particles. As more particles were formed, this
provided more opportunity for Mn(II) precursor to react along
with Pb(II). This allowed more particles got Mn doped. However,
it was indeed difficult to calculate the amount of Mn atoms
present per particle, rather its percentage as a whole was
assumed in all of our experiments. The function of RNH3Cl was
expected simply providing controlled amount of chloride as per
the demand of the reaction. More chlorinating agent means
more amount of supply of chloride ions and this helped reaching
the critical concentration for nucleation faster.
Correlating further the concentration dependency of
RNH3Cl for tailoring the Mn d-d emission, microscopic images of
all samples in presence and absence of RNH3Cl were analyzed.
Very interestingly, it was observed that for nanocrystals obtained
without RNH3Cl showed nanocubes having average diameter
~25 nm (Figure 3a), but a drastic reduction of size was noticed
in presence of RNH3Cl (Figure 3b,c and Figure S5). Further, it
was observed that with variation of the amount of RNH3Cl, the
average size of nanocubes varied. For 0.1 ml and 0.5 ml
RNH3Cl, approximately nanocubes having average edge length
~ 12 and ~ 8 nm were obtained. Histograms showing the size
distribution for these three sets of images are shown in Figure
S6. While, all these cases the reaction temperature was fixed at
Apart from typical cube shape, the doping was also
performed in platelet shaped CsPbCl3 nanostructures. While all
the above experiments were carried out with Cs to Pb precursor
ratio 1:5 and with 0.5 ml RNH3Cl; but interestingly, with 1:2 ratio
the shape turned to mostly 2D platelets. The TEM images and
XRD pattern obtained from the nanostructures are presented in
o
180 C, the size for the traditional reaction following ice cooling
approach under similar condition was also measured.
Interestingly, it was observed that the cube size maintained ~ 12
nm (Figure S7). Further, for understanding the role of Mn, all
the reactions were carried out without Mn which had similar
trend suggesting the amount of MnCl2 used here had no impact
either on the shape or the size. However, the contrasting
observation was noticed with prolonged annealing of the
nanocrystals. In absence of RNH3Cl these were turned to bulk
(Figure S8), but interestingly, in presence of RNH3Cl the size
remain unchanged. Figure 3d shows the TEM image of sample
obtained after 10 min of annealing from the reaction with 0.5 ml
RNH3Cl and the size was ~ 8 nm and this was same as in Figure
3c. The dark spot on the TEM images of these nanocubes are
the Pb(0) which were formed under electron beam and not in
Figure 4. (a) TEM image of stacked CsPbCl3 platelets. (b) Absorption and
PL spectra of Mn doped CsPbCl3 platelets. Inset shows the schematics of
platelet stacking. More TEM images are provided in Figure S8.
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10.1002/anie.201703863
Angewandte Chemie International Edition
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Figure 4a (also Figure S9) and Figure S10 respectively.
Platelets were observed stacked or self-assembled in the
images and these were also in cubic phase. The UV-visible and
PL spectra of these nanostructures are shown in Figure 4b
which shows intense Mn d-d emission, and the dual emission
ratio remained almost same like our best doped nanocubes with
5% Mn and 0.5 ml RNH3Cl.
The quantum yield (QY) of our best sample was 27 %
standardized following the procedure mentioned in our previous
report.[6b] We focused here the relative intensity ratios of the dual
emissions as the function of concentration of the additive salt
and hence different literature reported QYs were not compared.
In conclusion, a chemically controlled doping protocol is
reported for obtaining highly efficient Mn doped CsPbCl3
nanocrystals. Using RNH3Cl as the active chlorinating agent for
activating the reactivity of MnCl2 along with PbCl2 at elevated
temperature, the doped nanocrystals were synthesized where
the Mn d-d emission intensity wastuned as a function of amount
of RNH3Cl. As a consequence, only 5 to 10% Mn(II) precursor
became enough in obtaining the highquality doped nanocrystals
Analysis suggested that RNH3Cl helped in controlling the size by
increasing the number of particles which provided opportunity for
more Mn to react and got doped. Further, varying Cs to Pb
precursor concentration, doped 2D platelets were synthesized
which also retained the Mn emission. These suggest that
beyond the dopant-host precursors concentrations, manipulation
of the doping activating reagent can controllably tailor the dopant
emission intensities in perovskite host nanocrystals.
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Acknowledgements
DST of India (SJF/CSA-01/2010-11, SR/NM/NS-1383/2014) is
acknowledged for funding. SDA, SKD, AD, AKG acknowledge
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Keywords: CsPbCl3 • d-d emission • doped perovskites •
Mn:CsPbCl3 • platelets
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Layout 1:
COMMUNICATION
Programming Perovskite doping:
Controlled doping of Mn(II) in CsPbCl3
nanocrystals were performed by using
alkylamine hydrochloride (RNH3Cl) as
doping promoting reagent. The dopant
emission intensity is tailored as a
function of Mn doping governed by the
amount of introduced RNH3Cl. This
helped in stabilizing and also
S. Das Adhikari, S. K. Dutta, A. Dutta, A.
K. Guria, N. Pradhan*
Page No. – Page No.
Chemically Tailoring the Dopant
Emission in Mn doped CsPbCl3
Perovskite Nanocrystals
controlling the size of CsPbCl3
nanocrystals which in turned
facilitated efficient doping.
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