Materials Today Chemistry 23 (2022) 100753

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Materials Today Chemistry

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Impact of Zn-doping on the composition, stability, luminescence

properties of silica coated all-inorganic cesium lead bromide
nanocrystals and their biocompatibility
M.R. Kar a, R. Chakraborty b, U. Patel a, R. Chakraborty c, S. Ray a, T.K. Acharya b,
C. Goswami b, S. Bhaumik a, *
a
Department of Engineering and Materials Physics, Institute of Chemical Technology, IndianOil Odisha Campus, Bhubaneswar, Odisha, 751013, India
b
School of Biological Sciences, National Institute of Science Education and Research, Bhubaneswar, Odisha, 752050, India
c
School of Physical Sciences, Indian Association for the Cultivation of Science, Kolkata, West Bengal, 700032, India

a r t i c l e i n f o a b s t r a c t

Article history: Cesium lead halide (CsPbX3: X ¼ I, Br, Cl) nanocrystals (NCs) are believed to be potential candidates for
Received 18 October 2021 bioimaging applications. However, their low structural stability against polar solvents remains as a major
Received in revised form limitation. To improve the NCs stability and maintain high emission intensity, we synthesized silica
10 December 2021
coated Zn-doped core@shell perovskite NCs via modified ligand assisted reprecipitation (LARP) synthetic
Accepted 13 December 2021
Available online 17 January 2022
method under relatively high humid condition. We systemically varied the composition inside the
perovskite structure and then studied their photophysical properties and stability. Interestingly, the Zn-
doping amount controls the ratio of CsPbBr3 to Cs4PbBr6 perovskites inside the core and also facilitates
Keywords:
Cesium lead bromide perovskites
the growth of (OA)2PbBr4 shell, enables overall increase in NCs emission intensity and stability. We
Silica coated nanocrystals observed green color emission from these NCs in the spectral range of 494-506 nm with a maximum
Zn-doping photoluminescence quantum yield (PLQY) up to 88%. The optimized Zn-doped NCs exhibited nearly four
Stability times better water stability compared to the bare NCs and retain emission properties for several months
Biocompatibility even in highly polar solvents. Finally, we performed biocompatibility test of the NCs generated on bio-
logical samples and hydroponics test in a gardenia leaf for their potential bioimaging applications.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction lower light scattering at longer wavelengths making them ideal

for fluorescence imaging, photodynamic therapy, and three-
All-inorganic cesium lead halide (CsPbX3: X ¼ I, Br, Cl) dimensional (3D) data storing [8e10]. After the first report on
perovskite nanocrystals (NCs) have attracted immense attention the colloidal synthesis of CsPbX3 NCs by Protesescu et al. [11], in
in various optoelectronic applications owing to some of their 2015, various research activities are underway to improve the NCs
excellent photo-physical properties, such as high absorption co- crystallinity and quality; controlling the shape, size and compo-
efficient, color tunable emission spectra, bright luminescence, sition of the NCs; enhancement of PL intensity, color tunability,
narrow emission full-width half maxima (FWHM), high color stability; surface ligand engineering and so on [1,2,12e14]. The
purity, easy solution processability, and their dispersion in research has been extended to explore comparatively stable
various liquid media [1e5]. These perovskite NCs exhibit multi- lower-dimensional perovskite structures (2D, 1D, 0D), in which
photon absorption property up to five photon absorption which is [PbX6]4-octahedra are not connected in all three directions
more efficient compared to conventional dye molecules [6,7]. The [15e17]. Such lower-dimensional perovskite materials demon-
multiphoton absorption property allows photons to penetrate strate comparatively higher bandgap, high exciton binding en-
deeper inside the biomolecules, have better spatial selectivity and ergy, and better structural stability [15e18].
higher resolution, reduced sample damage and heating, and The perovskite NCs are mostly suffering from structural and
chemical instability because of their intuitive sensitivity to polar
solvents [19,20]. The perovskite NCs rapidly decompose or degrade in
* Corresponding author. the presence of polar solvents because of their strong ionic nature. To
E-mail address: s.bhaumik@iocb.ictmumbai.edu.in (S. Bhaumik). overcome such instability issues, different innovative strategies have

https://doi.org/10.1016/j.mtchem.2021.100753
2468-5194/© 2021 Elsevier Ltd. All rights reserved.
M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

been implemented to improve the stability of the perovskite struc- industry. The small size, tunable PL properties, excellent structural
ture. Doping of metal ions (Rb, K, Zn) into perovskite structures can and photostability, facile functionalization with biomolecules,
enhance structural stability by enhancing the formation energy and minimal cytotoxicity, and good biocompatibility of the nano-
can also increase emission intensity by improving the lattice quality particles (NPs) enable their exposure in the fields of plant research,
and suppressing the defects [21e23]. It has been seen that Zn-doped such as in-vivo or in-vitro imaging of plants, increasing the effi-
CsPbX3 NCs demonstrate better optoelectronic device performances ciency of photosynthesis, nanofertilizers, biosensors, and so on
than bare CsPbX3 NCs [24e26]. On one hand, the synthesis of [51,52]. Plant imaging is a useful tool to understand more about the
core@shell nanostructures is an effective way to further improve the plant cell structure, tissue formation, and nutrition transport
stability and reduce the non-radiative recombination processes through the stems [51]. Si, Zn, Au, Fe NPs are proved to act as
[27e31]. On other hand, water stability of the NCs can be improved nanofertilizer that not only improve the quality and also yield of
through the coating of bulky organic ligands, polymers, silica, high crop production but also increase the resistance of the plants
bandgap oxide layer (TiO2, Al2O3, ZnO), inorganic sulfide layer (ZnS, against various diseases [53]. C and Si NPs are extensively used in
CdS, PbS, PbSe), perovskite shell, and/or superhydrophobic frame- biomonitoring, biosensing, drug delivery, photocatalysis applica-
work structures [27,28,32e35]. Such high bandgap shell materials tion [54].
can protect the core materials from the ambient environment and Here, in this work, we aim to synthesize comparatively stable
also prevent oxygen and water molecules to diffuse inside the core NCs that can be transferred to polar solvents for bioimaging
that enables an overall increase in material stability. This core@shell application in plant cells which needs excellent water stability from
structure also helps to confine the electrons and holes inside the core the NCs. We report first time synthesis of highly luminescent silica-
material, allowing efficient exciton recombination and enhancing the coated Zn-doped CsPbBr3eCs4PbBr6 nanocomposite core and
emission intensity [27,28]. Bhaumik et al. reported a novel protocol (OA)2PbBr4 shell perovskite NCs via LARP synthetic approach. We
for the synthesis of core@shell NCs with 3D methylammonium lead found that the Zn-doping can control the ratios of CsPbBr3 to
bromide (MAPbBr3) perovskite core and layered octylammonium Cs4PbBr6 perovskite structures inside the core material and further
lead bromide [(OA)2PbBr4] perovskite shell, demonstrates better improve the PL intensity and stability. The emission spectra of these
structural stability and higher luminescence intensity that can sustain NCs were located in the spectral range of 494e506 nm and had a
for several months [36]. Color tunable CsPbX3@Cs4PbX6 and green- maximum PLQY of up to 88%. The NCs had a size distribution in the
emitting CsPbBr3@Rb4PbBr6 core@shell NCs were also synthesized range of 5e40 nm, and the particles become more uniformly
via a hot-injection method that is highly luminescent and exhibit distributed upon Zn-doping. The doped NCs demonstrated excel-
superior photostability [37,38]. However, it's very challenging to lent stability in water nearly four times compared to undoped NCs,
synthesize pure CsPbBr3 NCs via the ligand-assisted reprecipitation which is a prerequisite for bioimaging applications. Finally, the first
(LARP) synthetic method. Here some unwanted Cs4PbBr6 phases also time we observed the uptake of these NCs by live mammalian cells
grow and forms CsPbBr3eCs4PbBr6 nanocomposites, which is detri- and Gardenia jasminoides leaf, highlighting their biocompatibility.
mental for the synthesis of highly luminescent NCs [39,40].
Silica-coated perovskite NCs show better stability even in 2. Results and discussion
water media because of their higher resistance against moisture
[41]. Recently, several research articles have been reported on The detailed synthesis procedure of the silica-coated perovskite
silica-coated CsPbX3 NCs synthesized from different silica sour- NCs is discussed in the experimental section in the Supporting
ces, such as (3-aminopropyl) triethoxysilane [APTES], (3-amino- Information part. We have selected APTMS for the silica source
propyl)trimethoxysilane [APTMS], tetraethylorthosilicate, or because the alkoxy groups have less steric hindrance because of
tetramethoxysilane [27,28,42]. The absence of amino groups in their shorter chain length than APTES, allowing faster reaction for
tetraethylorthosilicate and tetramethoxysilane require additional growth of silica coating around the perovskite NCs [46]. The APTMS
ligands for controlling the reaction kinematics and shape of the has dual functions as it binds the NCs surface with its amino groups,
perovskite NCs during the synthesis [41,43]. These silica sources and the alkoxysilane groups hydrolyze to form silanol groups in
are usually used to grow mesoporous structures that can overall presence of a trace amount of water as shown in the schematic
increase the NCs surface [44]. Such mesoporous silica NCs are diagram Fig. 1a [42]. Further condensation of silanol groups forms a
used for drug delivery which can render a high payload of the silica coating around the NCs as a silica matrix. The higher chemical
drug [45]. However, the APTMS and APTES ligand helps growth of activity element, i.e. Zn-ions partly substitute the Pb-ions in the
compact thick shells around the core materials that can prevent perovskite structure as represented in schematic diagram Fig. 1b
degradation of the core against environmental moisture and [24]. The high bandgap (OA)2PbBr4 shell around the core (see
oxygen [46]. The presence of amino groups in these ligands schematic diagram Fig. 1c) facilitates effective radiative recombi-
effectively passivate the NCs surface, and the silyl groups hy- nation of excitons in the core and increases NCs emission intensity
drolyze to form a cross-linked matrix around the NCs that helps and stability [36]. We synthesized silica-coated methylammonium
to improve NCs stability and PL intensity [42]. Such silica-coated lead bromide (MAPbBr3) and MAPbBr3@(OA)2PbBr4 core@shell
perovskite NCs maintain their initial luminesce even in water perovskite NCs via a conventional LARP synthetic approach. We
media and demonstrate excellent stability, enable them to use as noticed that the water stability of such hybrid perovskite NCs is
bioprobes for cell imaging and biomedical applications very poor (see supporting information part). It is well known that
[42,47,48]. Recently, Kumar et al. [49] revealed that the all inorganic CsPbBr3 perovskites are more stable than organic-
CsPbBr3@SiO2 core@shell NCs are non-toxic in nature, and they inorganic MAPbBr3 counterparts against moisture, heat, and pho-
are suitable for in-vitro cell imaging using HeLa cells. Chen et al. toirradiation [55]. So, we focused our synthesis on comparatively
[50] further encapsulated SiO2-coated CsPbBr3 NCs with phos- stable silica-coated CsPbBr3eCs4PbBr6@(OA)2PbBr4 NCs and then
pholipid micelles and implemented them in targeted single and varied Zn-doping concentration inside the core. Such core@shell
multiphoton imaging of cancer cells. These observations inspire perovskite NCs exhibit better stability with improved luminescence
researchers to work and explore all-inorganic perovskite nano- intensity and retain their luminous properties for several months
composites in the field of live-cell imaging. even in polar solvents. For better understanding, we rename the
Nanomaterials are also believed to play an important role in silica-coated CsPbBr3eCs4PbBr6@(OA)2PbBr4 core@shell NCs as
overcoming the current challenges faced by the agriculture NCs-0 through over the manuscript. Similarly, 20%, 40%, 60%, and
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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

Fig. 1. Schematic representations of (a) hydrolysis and condensation processes of APTMS for silica shelling around the perovskite NCs, (b) Zn-ions substitution in the place of Pb-
ions in a CsPbBr3 perovskite crystal structure, and (c) a 3D@2D perovskite core@shell structure. 2D, two-dimensional; 3D, three-dimensional; APTMS, (3-aminopropyl)
trimethoxysilane.

80% Zn-feeding in NCs-0 are renamed as NCs-20, NCs-40, NCs-60, phases, i.e. 3D monoclinic CsPbBr3 phase and 0D rhombohedral
and NCs-80, respectively. Cs4PbBr6 phase [56,57]. Similar mixed-phase NCs were previously
The X-ray diffraction (XRD) patterns of all the NCs samples in observed when the CsPbBr3 NCs were synthesized via the LARP
the thin-film form are shown in Fig. 2a. The XRD diffraction pattern synthesis method [39,58,59]. The characteristic XRD diffraction
of NCs-0 reveals that the crystal structure is a mixture of two peaks at the angles of 15.03 , 21.33 , 30.13 , 34.29 , 37.52 , and

Fig. 2. Stacked XRD diffraction patterns of (a) different compositions of perovskite NCs, and (b) zoomed image of these NCs, as represented in legends. The bottom of (a) represents
the standard XRD diffraction patterns of rhombohedral Cs4PbBr6 (JCPDS no. 01-073-2478) and monoclinic CsPbBr3 (JCPDS no. 00-018-0364) perovskite structures. NCs, nanocrystals;
XRD, X-ray diffraction.

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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

Fig. 3. (a) TEM, (b) HRTEM images, and (c) SAED pattern of NCs-0. (d) TEM, (e) HRTEM images, and (f) SAED pattern of NCs-40. HRTEM, high-resolution transmission electron
microscopy; SAED, selected area electron diffraction; TEM, transmission electron microscopy.

43.97 ; correspond to (001), (110), (002), (201), (211), and (202) The NCs size, shape, and presence of silica coating were inves-
lattice planes, respectively, for the monoclinic CsPbBr3 phase (PDF tigated from high-resolution transmission electron microscopy
#00-18-0364) [39,58,59]. In addition, some other significant peaks imaging. The transmission electron microscopy (TEM) and high-
were also observed at 12.48 , 19.9 , 22.23 , 25.24 , 27.33 , 28.42 , resolution transmission electron microscopy images of NCs-0 are
30.12 , 33.49 , 38.85 , 40.65 , and 45.57 ; which correspond to represented in Fig. 3a,b. These images revealed that the NCs had a
(012), (113), (300), (024), (131), (214), (223), (321), (324), (226), and particle size distribution in the range of 5e40 nm with a mean
(600) lattice planes, respectively, of rhombohedral Cs4PbBr6 phase particle size of 10.11 ± 5 nm. The little blurred surface around the
(PDF #01-73-2478) [56,60]. Increasing the Zn-doping concentra- NCs appeared from the adsorption of silica encapsulation. This
tion in NCs-0, the XRD peak intensities of rhombohedral Cs4PbBr6 silica coating around the NCs was compact with a thickness of few
crystal phase was decreased successively. A similar observation was nm, preventing direct contact with the harsh outside environment
previously observed in CsPbBr3 NCs for doping with different ma- and maintaining high NCs stability. These NCs exhibited inter-
terials [61]. Moreover, the diffraction peaks shifted slightly to planar spacing of 0.66 nm (see Fig. 3b) that corresponds to (001)
higher angles with an increase in Zn-doping concentration (see lattice planes for monoclinic CsPbBr3 phase [56]. However, with Zn-
Fig. 2b), which indicates shrinkage in the perovskite crystal lattices doping (NCs-40) the particle size slightly increased and size dis-
due to substitution of Zn-atoms at Pb-lattice places [24]. However, tribution became more uniform, which is favorable for various
with excess Zn-feeding in the NCs, the successive XRD peaks shifted optoelectronic applications as shown in Fig. 3d,e [24]. The inter-
to lower angles that could be due to the introduction of interstitial planar spacing of NCs-40 slightly reduced to 0.65 nm (see Fig. 3e)
Zn-ions and causing lattice expansion [62]. The presence of because of the contraction of perovskite crystal lattices. This lattice
(OA)2PbBr4 crystal phase is not detected, which may be due to the contraction happened because of the smaller atomic radius of Zn-
formation of very thin layered shells around the core material [36]. ions (74 p.m.) that replace the interstitial Pb-ions (119 p.m.) [24].
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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

Fig. 4. (a) FTIR spectra of NCs-40. (b) Core XPS spectra of NCs-0 and NCs-40 as shown in legends. High resolution XPS spectra of (c) Zn 2p, (d) Pb 4f, and (e) Br 3d states, of NCs-0 and
NCs-40 as shown in legends. NCs, nanocrystals; FTIR, Fourier transform infrared; XPS, X-ray photoelectron spectroscopy.

The TEM images of NCs-20, NCs-60, and NCs-80 and particle size reduced the NCs luminescence intensity [13]. However, with
distribution of all NCs samples are represented in Figs. S1 & S2, optimal Zn-doing (NCs-40), the Pb:Cs atomic ratios of the NCs were
respectively (see Supporting Information part). The selected area maintained to 1:1, which overall facilitates to improve the NCs
electron diffraction patterns of NCs-0 (see Fig. 3c) and NCs-40 (see emission intensity and structural stability.
Fig. 3f) show the high crystallinity of perovskite NCs. The atomic We also performed the Fourier transform infrared spectroscopy
ratios of all the NCs were evaluated from energy-dispersive X-ray analysis to confirm the silica coating around the NCs (see Fig. 4a).
spectroscopy (EDS) measurements, shown in Fig. S3 and corre- The Fourier transform infrared spectroscopy spectrum for all the
sponding results are shown in Table S1 (see Supporting Informa- NCs showed similar patterns for the formation of the same silica
tion). EDS measurements indicated the presence of Si- and O- coating. The spectrum revealed strong absorption peaks located at
atoms, confirming the silica coating around the NCs. It was noticed 1099 and 756 cm1, corresponding to the antisymmetric stretching
that the atomic ratios of Pb:Cs for NCs-0 is close to 2.55:1, ideally vibration peak of SieOeSi bonds and symmetrical stretching vi-
which should be close to 1:1. The excess Pb-contents in NCs- bration peaks of SieO bonds, respectively [42,46]. The additional
0 resulted in the formation of deep trap states and overall peaks at 3,435, 2,923, and 2,854 cm1 appeared because of the

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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

Fig. 5. (a) UVevis absorption spectra, (b) PL spectra, and (c) water stability test of different Zn-doped perovskite NCs, as represented in legends. Inset of (b) represents the
photographic image of these NCs dispersed in ethanol solvent and placed under a UV lamp. NCs, nanocrystals; PL, photoluminescence; UVevis, ultraviolet-visible.

antisymmetric stretching vibration of eOH bonds, the asymmetric, The increase in binding energies of Pb 4f5/2 state (~0.3 eV) and Br
and symmetric stretching vibration of CeH bonds, respectively. The 3d3/2 state (~0.4 eV) of NCs-40 in comparison with undoped NCs,
enrichment of SieOeSi, SieO vibration peaks indicate the silica reveal the stronger PbeBr interaction in the Zn-doped NCs. The XPS
coating is formed around the NCs after the hydrolysis process. We signal peaks of Cs 3d, C 1s, N 1s, and O 1s chemical states are shown
noticed that the peaks at 3,208 cm1 and 1,580 cm-1 correspond to in Fig. S4 (see supporting Information part). The additional signal at
NeH stretching and NeH bending vibrations, respectively, and also, 401.7 eV and a minor hump at 408 eV appeared due to the amine
NeH stretching vibrations (3,350-3,310 cm1) were shifted toward groups present in the (OA)2PbBr4 layer (see Fig. S4c, supporting
lower frequencies, indicating the presence of (OA)2PbBr4 shell [63]. information part) [63]. However, for the NCs-40 samples, the peak
To further explore the presence of Zn-doping and also understand intensities were improved and slightly shifted to lower energies,
the interaction of ions before and after the addition of Zn ions, the suggesting better binding of (OA)2PbBr4 layer to the core NCs with
X-ray photoelectron spectroscopy (XPS) measurement was con- Zn-feeding.
ducted for NCs-0 (without Zn-doping) and NCs-40 (with Zn- The UV-VIS absorption spectra of all the NCs are shown in
doping) samples. The corresponding full XPS patterns are shown Fig. 5a. The absorption spectrum for NCs-0 revealed two significant
in Fig. 4b. The Fig. 4c-e represent the excited XPS peaks of Zn 2p, Pb absorption peaks, one was in the visible region and another one in
4f, and Br 2p chemical states, respectively. In Fig. 4c, two additional UV spectral region. A band edge absorption peak close to 507 nm
peaks of Zn 2p states appeared at 1,022.3 eV (2p3/2) and 1,045.6 eV appeared because of the presence of CsPbBr3 perovskites structures
(2p1/2) in NCs-40 compared to undoped NCs-0, confirming the [11,66]. We could not detect any change in absorption peak position
presence of Zn-ions in doped NCs [24,64]. The Fig. 4d shows Pb 4f for other NCs. With higher Zn-feeding concentration, the absorp-
signal peaks located at 138.7 eV (4f7/2) and 143.7 eV (4f5/2) for NCs- tion peak became sharper due to better NCs size distribution as
0, while Fig. 4e displays Br 3d single signal peak positioned at
68.8 eV (3d3/2). However, with Zn-feeding in the NCs (for NCs-40),
the corresponding signal peaks of Pb 4f signals (4f5/2 and 4f7/2) and Table 2
Br 3d signals (3d3/2) were shifted toward higher energies [25,65]. Water stability tests of different silica coated Zn-doped NCs.

Sample Name The amount of water required (mL)

Table 1 Transition from green to blue No emission

Optical properties of different silica coated Zn-doped NCs. emission color

MAPbBr3@SiO2 30 90
Sample Name Absorption edge position PL peak position (nm) PLQY (%)
MAPbBr3/(OA)2PbBr4 @SiO2 50 100
(nm)
CsPbBr3@SiO2 60 100
NCs-0 507 494 63 NCs-0 170 250
NCs-20 512 506 81 NCs-20 210 360
NCs-40 507 508 88 NCs-40 230 380
NCs-60 508 503 78 NCs-60 190 350
NCs-80 509 506 66 NCs-80 170 280

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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

seen from our TEM imaging and also reduced the scattering effect. The PL emission spectra of the NCs are represented in Fig. 5b.
In addition, a strong absorption peak at around 320 nm was The photographic image of all these NCs under UV lamps are
detected that is attributed due to the presence of Cs4PbBr6 perov- shown in the inset of Fig. 5b. The emission peak position of NCs-
skite structures, which originated from optical transitions between 0 was obtained at 494 nm (FWHM~ 34 nm). With increasing the
localized states of isolated [PbBr6]4- octahedra [67]. However, the Zn-doping concentration in NCs-0, the PL spectrum was first red-
absorption peak position (~320 nm) in UV spectral region remained shifted up to a certain level of Zn-doping concentration (of 40%)
unchanged with Zn-doping concentration because the Cs4PbBr6 because of an increase of NCs size distribution as already observed
perovskite structure remains unaffected after doping. However, the from TEM imaging. However, with a higher Zn-feeding concen-
absorption peak intensity decreased with higher Zn-doping con- tration (more than 40%), the PL spectrum was blue-shifted
centration because of an overall reduction in Cs4PbBr6 phases than because of the increase in bandgap energy that appeared from
CsPbBr3 phases. These observations confirm that with an increase crystal lattice contraction [24]. The PL intensity also raised to a
in the Zn-feeding concentration, there is a reduction in 0D perov- certain Zn-doping concentration (of 40%) and then it decreased
skite phases and an increase in 3D perovskite phases, which re- with further doping amount. The Zn-doped NCs exhibited PL peak
sembles our observations from XRD measurements. In addition, a positions in the spectral range of 494e506 nm. In addition, two
small hump was detected at around 410 nm for the NCs-20, NCs-40, small humps appeared in the spectral range of 395e435 nm that
NCs-60, and NCs-80 signifies the (OA)2PbBr4 shell formation originated from the recombination of excitons in layered perov-
around the core NCs. So, the Zn-ions facilitate the growth of thicker skite structures [17,36]. The emission PLQY of NCs-0 and NCs-40
(OA)2PbBr4 shell around the core that passivates the NCs surface were calculated to be around 63% and 88%, respectively. The
and maintain high PL intensity and stability of the NCs. subsequent information regarding absorption edge, PL peak

Fig. 6. Biocompatibility of NCs-40 with mammalian cells. NCs (blue) are internalized by cells and do not associate with both mitochondria (green) and lysosomes (red). Higher
concentration of NCs have a detrimental effect on cells-mitochondrial and lysosomal structures become atypical. NCs, nanocrystals.

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M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

position and PLQYs of all samples are provided in Table 1. These performed these tests for silica-coated MAPbBr3 and MAPb-
results can be directly correlated to the reduction of Cs4PbBr6 Br3@(OA)2PbBr4 NCs, which showed very poor emission stability in
phases with an increase in Zn-doping concentration in the core water and the NCs degraded very fast even addition of a small
and also facilitate the growth of (OA)2PbBr4 shell around the amount of water. However, silica-coated CsPbBr3 and
perovskite core, that overall increase the efficient exciton CsPbBr3@(OA)2PbBr4 NCs showed better stability against the water.
recombination inside the core and hence improve NCs emission The NCs stability further improved with Zn-doping which is
intensity. However, the higher Zn-feeding (more than 40%) favorable for bioimaging applications. The NCs-40 showed the best
resulted in an excess substitution of luminescent centers in the water stability against the water among all other NCs, in which
perovskite lattice and also formed trap/defects states for inter- 230 mL of DI water was required to transform from green emission
stitial Zn-ions, resulting in a reduction of NCs emission intensity to blue emission color. However, with the addition of 380 mL of DI
[24,62]. The emission FWHM became narrower for doped NCs due water, the luminance of NCs-40 was totally quenched. The subse-
to better NCs size distribution as already seen from TEM images quent observations are provided in Table 2.
[24]. These results signify that the proper doping amount in the We further investigated the potential use of these NCs in bio-
NCs can enhance the optical properties. Furthermore, we per- logical samples using live-cell microscopy (see Fig. 6). Toward this,
formed time-resolved PL measurements to understand the the Chinese Hamster Ovary cell line (CHOeK1) mammalian cell was
exciton recombination dynamics in the NCs. The experimental used for NCs treatment at two different dilutions- 1:50 and 1:100.
time-resolved PL decay curves were fitted with bi-exponential We observed uptake of NCs-40 in both the dilutions tested. To
decay functions (see Fig. S5 in supporting information part). The check for their potential interactions with subcellular organelles,
decay curves were nearly similar and the average lifetime of the we co-stained the cells for mitochondria and lysosomes. The NCs
samples had no significant change suggesting that the exciton have not been observed to interact with these organelles. However,
recombination dynamics are not much affected by Zn-doping. both mitochondrial and lysosomal structural integrity, as well as
It has been observed that the silica coating around the NCs helps intensity, were distorted at a higher concentration of these NCs.
to stabilize the core material against environmental degradation Lysosomes and mitochondria are important cell organelles that
[46]. We performed the water stability test for our NCs, which is the regulate cellular function and metabolism. Mitochondria is the
first requisite for bioimaging application, and corresponding known powerhouse of the cell and controls cellular energy meta-
photographic images are represented in Fig. 5c (detail information bolism, and on the other hand, lysosomes detoxify the cellular
in Figs. S6 and S7, see supporting Information)[68]. First, we took environment. In our findings, we noticed that in low concentration
100 mL of each NCs solution in ethanol (concentration of ~10 mg/ of NCs ware accumulated inside the cytoplasm and had no toxic
mL) and then added 10 mL of deionized (DI) water in sequence. We effect on the cellular structures though higher concentration of NCs
monitored the amount of DI water required to change the emission showed a potentially toxic effect on the cellular organelles. Here,
properties of the NCs in presence of water molecules via two we can observe that these NCs can be used for potential bioimaging
conditions. In the first case, we recorded the amount of DI water purposes at the lower concentration.
required to transform the emission color of the NCs from green to Finally, we investigated the intake process of our NCs in the
blue color under a UV lamp, which is happened due to the con- plant cells which is a crucial point for plant imaging application
version of CsPbBr3 perovskite structures to lower-dimensional [70]. We took NCs-40 in ethanol solvent (concentration of ~5 mg/
perovskite structures after the crystal degradation process [69]. In mL) and a gardenia leaf with a flower for the hydroponics experi-
the second case, we recorded the amount of DI water required to ment. The gardenia plant stem (leaf and flowers attached, see
complete degradation of perovskite structures, i.e. the luminesce Fig. 7a) was dipped in the NCs solution and kept under normal
from NCs was un-detectable or fully diminished. We also atmospheric conditions (relative humidity level above 50%). After

Fig. 7. The photographic images of (a) gardenia stem (containing leaf and flower) dipped in NCs-40 containing ethanol solution. Leaf and flower images (b) under normal day light
after 1 day, (c) under a UV light after 1 day. Leaf image (d) under normal day light after 2 days, (e) under a UV light after 2 days, (f) under normal day light after 7 days, and (g) under
a UV light after 7 days. NCs, nanocrystals; UV, ultraviolet.

8
M.R. Kar, R. Chakraborty, U. Patel et al. Materials Today Chemistry 23 (2022) 100753

one day, we observed that a certain portion near the leaf base and Manav Raj Kar and Urjjarani Patel did the hydroponics test in a
the stalk of the flower were luminescent under a UV lamp (see leaf.
Fig. 7c). On closer look, we found that some of the upper parts of the Raja Charkraborty characterized some of UV-VIS, PL and XRD
leaf veins were also weakly luminescent. In addition, we found that measurements.
the portion of the leaf stem and base that dipped in ethanol solu- Ranabir Chakraborty and Tuser Kanta Acharya performed the
tion turned slightly brown color under visible light and pinkish-red bioimaging part.
under the UV light which is due to the damaging of plant cells in All authors discussed with others and analyzed the data.
contact with ethanol (see Fig. 7b) These observations confirm the All authors contributed in the manuscript writing.
successful intake of the NCs solution through the plant stem, Dr. Saikat Bhaumik lead the project.
traveled through the leaf veins, and deposited in the leaf veins and
leaf lamina. After two days, the luminescent area on the leaf surface Declaration of competing interest
was reduced due to the degradation of perovskite materials, and
the flowers wilted and fell off from the stem (see Fig. 7d,e). So, we The authors declare that they have no known competing
continued our experiments with the leaf only (for detailed infor- financial interests or personal relationships that could have
mation, see Figs. S8 & S9 in supporting information). Interestingly, appeared to influence the work reported in this paper.
even after seven days, the surface of the leaf along with the veins
and mid-rib, where the NCs are deposited, looked fresh and green
Acknowledgments
(see Fig. 7f,g). However, other parts of the leaf turned brown color
and dried as well. It may be happened due to the lower cytotoxicity
S. B. acknowledges to Department of Science and Technology
and better biocompatibility of silica-coated NCs with plant cells
(DST), India (Award number# DST/INSPIRE/04/2017/000530) and
that reduce the aging and wilting processes of the leaf. These re-
ICT-IOC startup research grant for the financial support. U. P. thanks
sults are extremely valuable in studying the interaction of perov-
to DST, India for fellowship support. S. B. acknowledges to NCL Pune
skite NCs with plant cells and further imaging application to detect
for support in HRTEM and XPS characterizations. C. G. thanks
different cells.
NISER, Bhubaneswar for its intramural support to carry out this
work. C. G. also thankful to NISER imaging facility.
3. Conclusions
Appendix A. Supplementary data
In summary, we report the synthesis of silica-coated core@shell
perovskite NCs via the modified LARP method and subsequently Supplementary data to this article can be found online at
varied the Zn-doping concentration inside the NCs. Here, we used https://doi.org/10.1016/j.mtchem.2021.100753.
APTMS as a source of silica shell that helps to disperse the NCs even
in polar solvents. The compact and thick silica shell protects from References
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