DOI: 10.1002/slct.

201700518 Full Papers

1
2 z Inorganic Chemistry
3
4
5
Synthesis of Hybrid to Inorganic Quasi 2D-Layered
6 Perovskite Nanoparticles
7
8 Muhammad Aamir,[a, b] Malik Dilshad Khan,[a] Muhammad Sher,[b] Mohammad Azad Malik,[a, c]
9 Javeed Akhtar,*[d] and Neerish Revaprasadu*[a]
10
11
12
Metal halide perovskites have emerged as a potential candidate violet-visible spectroscopy (UV/Vis). Transmission electron mi-
13
for photovoltaic and light emitting applications. Tuning the croscopy (TEM) showed that the shape of the as-prepared
14
optical properties by tailoring the perovskite nanostructures nanostructures can be tuned from rectangle/rods to sheet like
15
could enhance the efficiency of these devices. Herein, we structures. It was observed that the ratio of the organic cation
16
report the synthesis of hybrid to inorganic quasi-2D perov- (anilinium ion) plays a crucial role in the development of the
17
skites, by using different ratios of PhNH3Br and CsI, to prepare perovskite crystallites size and shape. This is the first such study
18
(Cs)x(PhNH3)2-2xPbBr4-xIx nanomaterials. The as-prepared nano- on the conversion of hybrid 2D perovskite to inorganic quasi-
19
structures were characterized by powder X-ray diffraction (p- 2D perovskite by using inorganic cation (Cs +) and could be a
20
XRD), Fourier transform infrared spectroscopy (FTIR) and ultra- potential material for optoelectronic applications.
21
22
perovskite material depend on the dimensions of the inorganic
23 Introduction
framework. The size and conformation of the R cation plays a
24
Lead halide perovskite materials have received attention due to critical role in determining the dimensions of the inorganic
25
their potential for various applications including solar cells,[1] framework to produce 3D, 2D and 1D perovskite materials.[12].
26
light emitting diodes,[2] lasers,[3] photocatalysis[4] and sensing[5] Low dimensioned perovskites show increased exciton bind-
27
owing to their excellent optical and electronic properties.[1a] ing energy, reduced fluorescence decay times and enhanced
28
However, intensive studies are underway to improve stability,[6] optical properties due to the quantum confinement of
29
environmental compatibility,[7] process reproducibility[8] and to electrons and holes as compared to 3D perovskites.[13] In
30
develop photophysical mechanisms.[8b,9] addition, the exciton is likely to be more stable in low
31
The organic inorganic perovskites show a quantum well dimensional perovskites. The optical and electrical properties
32
structure where the organic cations act as barriers and the can be tuned by changing the organic components, inorganic
33
inorganic metal halides form a quantum well.[10] The organic components or their relative abundance.[14] The band gap is
34
inorganic perovskite has a general formula of (R*)2(R)n-1MnX3n + 1 increased when moving from 3D to 2D perovskite.
35
where R* and R are organic/inorganic cations, M is a divalent To synthesize low dimensional perovskites, substitution of
36
metal and X is a halide ion.[11] The large sized R* organic cations the methyl ammonium cations with large sized organic cations,
37
separated by the MX6 layers determine the number of leads to an increase in the exciton binding energy by more
38
perovskite layers and convert the 3D structures to 2D or a than 200 meV.[15] Recently, quasi-2D perovskite solar cells have
39
mixture of 2D and 3D (quasi-2D). The dimensions of the been reported based on methylammonium and alkylammo-
40
nium cations with improved moisture stability.[16] Hamaguchi
41
et al. have reported the cyclohexylammonium and cesium
42 [a] M. Aamir, M. D. Khan, Dr. M. A. Malik, Prof. Dr. N. Revaprasadu
University of Zululand, Private Bag X1001, Kwadlangezwa, 3886. South based qusai-2D perovskite solar cell. However, lower PCE was
43
Africa observed with enhanced stability.[17] However, the use of Cs and
44 Phone: + 27 35 902 6152 anilinium cations to synthesize low dimensional perovskites has
45 Fax: + 27 35 902 65681
never been reported.
46 E-mail: RevaprasaduN@unizulu.ac.za
[b] M. Aamir, Dr. M. Sher Herein, we report the one-pot synthesis of qusai-2D layered
47
Department of Chemistry, Allama Iqbal Open University, Islamabad, Paki- lead halide perovskite nanoparticles using cesium inorganic
48 stan cation and anilinium organic cation with tunable optical
49 [c] Dr. M. A. Malik
properties. By changing the concentration of the organic
50 School of Materials, The university of Manchester, Oxford Road, United
Kingdom, M13 9PL. anilinium cation and cesium cation, a series of 2D, quasi-2D
51
[d] Dr. J. Akhtar and 3D perovskite geometries have been obtained. The as-
52 Department of Physics, Nanoscience and Materials Synthesis Lab (NMSL), prepared perovskite nanoparticles have a general formula of
53 COMSATS, Institute of Information Technology (CIIT), Chak Shahzad, Isla-
(Cs)x(PhNH3)2-xPbBr4-xIx. The use of the anilinium organic cation
54 mabad, Pakistan.
E-mail: javeedk@comsats.edu.pk for the preparation of 2D layered perovskites has never been
55
Supporting information for this article is available on the WWW under reported. In the present study, a mixture of organic and
56
https://doi.org/10.1002/slct.201700518 inorganic cations has been used for the conversion of 2D
57

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layered hybrid lead halide perovskite to hybrid qusi-2D and to
1
3D inorganic perovskites.
2
3
4 Results and Discussion
5
The perovskite nanoparticles with varying composition synthe-
6
sized in this study, can be represented by the chemical formula
7
(Cs)x(PhNH3)2-2xPbBr4-2xIx. These derivatives were synthesized by
8
a wet chemical method using oleylamine and oleic acid as
9
capping agents. To manipulate the ratio of organic cations in
10
the perovskite structure, the PhNH3Br was prepared by treating
11
aniline with a slight excess of hydrobromic acid in ethanol at
12
0 8C, followed by evaporation under vacuum. The CsI is used
13
for the conversion of layered 2D hybrid (PhNH3)2PbBr4
14
perovskites to quasi 2D to inorganic 3D perovskites (Cs)x
15
(PhNH3)2-2xPbBr4-2xIx.
16
Figure 1 shows the comparison in p-XRD spectra of as
17
synthesized 2D (PhNH3)2PbBr4 nanoparticles and its starting Figure 2. Comparative p-XRD patterns of (Cs)x(PhNH3)2-2xPbBr4-2xIx derivatives
18 with increasing concentration of CsI and decreasing concentration of PhNH3
19 Br.
20
21
22
precursors which indicate that the 2D layered hybrid perovskite
23
(PhNH3)2PbBr4 has been successfully synthesized.
24
To explore the structural changes in the 2D hybrid
25
perovskite (PhNH3)2PbBr4, we performed two set of experiments
26
by varying the concentration of PhNH3Br and/or CsI. In the first
27
set of experiments, the concentration of CsI was increased by
28
20 % whereas the concentration of PhNH3Br was also decreased
29
by the same amount i. e. 20% to maintain the perovskite
30
stoichiometry.
31
Figure 2 shows the p-XRD with increasing concentration of
32
CsI and decreasing concentration of PhNH3Br to prepare
33
different (Cs)x(PhNH3)2-2xPbBr4-2xIx derivatives. The results are
34
summarized in Table 1. It can be observed that with the
35
addition of 20 % CsI (1.6:0.2:1 molar ratio of PhNH3Br:CsI:PbBr2),
36
the peaks at 2q = 11.70, 13.90 and 43.238 of (PhNH3)2PbBr4
37 Figure 1. Comparative p-XRD patterns of (a) PhNH3Br, (b) CsI, (c) PbBr2 and
disappear and the new diffraction peaks located at 2q = 15.26,
38 (d) (PhNH3)2PbBr4.
21.58, 30.77, 34.47, 37.88 and 43.878 appear which belong to
39
the orthorhombic phase (ICDD 01–072-7929) of perovskite.
40
Further experiments were performed in which the concentra-
41
precursors. To confirm the formation of 2D material (PhNH3)2 tion of CsI was increased to 40%, 60%, 80% and 100%,
42
PbBr4, the diffraction peaks of the as-prepared material were meanwhile decreasing the concentration of PhNH3Br by same
43
compared to the diffraction patterns of PhNH3Br and PbBr2. The amount with respective 1.2:0.4:1, 0.8:0.6:1, 0.4:0.8:1 and 0:1:1
44
diffraction peaks at 2q = 11.70, 13.90, 15.07, 21.32, 30.34, 33.83 molar ratios for PhNH3Br:CsI:PbBr2. However, it was observed
45
and 43.23 does not match with the diffraction peaks of that the phase of (Cs)x(PhNH3)2-2xPbBr4-2xIx derivatives remained
46
the same.
47
48
49
Table 1. Effect of composition on phase in as-prepared perovskites.
50
51 Perovskite nanoparticles Concentration of A site cations Phase
52 (PhNH3)2PbBr4 X = 0.0 Layered
53 (Cs)0.2(PhNH3)1.4PbBr3.6I0.2 X = 0.2 Orthorhombic
54 (Cs)0.4(PhNH3)1.2PbBr3.2I0.4 X = 0.4 Orthorhombic
55 (Cs)0.6(PhNH3)0.8PbBr2.8I0.6 X = 0.6 Orthorhombic
(Cs)0.8(PhNH3)0.4PbBr2.4I0.8 X = 0.8 Orthorhombic
56 (Cs)1PbBr2I1 X = 1.0 Orthorhombic
57

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Based on the above discussions, it can be concluded that formation of the monoclinic phase is not clear; it may be due
1
the orthorhombic phase is more stable and the perovskite is to the presence of phenylammonium ion and temperature.
2
converted from a 2D perovskite to 3D perovskite. The p-XRD of Interestingly, when the concentration of CsI was increased up
3
the as prepared (Cs)x(PhNH3)2-2xPbBr4-xIx derivatives with the first to 40%, the cubic phase of (Cs)0.4(PhNH3)1.6PbBr3.6I0.4 perovskite
4
set of experiments does not show any clear geometrical developed (1.6:0.4:1 molar ratio of PhNH3Br: CsI:PbBr2). Similarly,
5
changes. Therefore, we performed a second set of experiments (Cs)0.6(PhNH3)1.4PbBr3.4I0.6 and (Cs)0.8(PhNH3)1.2PbBr3.2I0.8 also show
6
in which the concentration of PhNH3Br was halved (10 %) by the cubic phase (ICDD: 00–054-0752).
7
keeping CsI concentration same as in first set of experiments It may be concluded from the above discussions that with
8
and then studied their structural changes by p-XRD analysis as the increasing concentration of Cs + ion, the phase changes
9
shown in Figure 3 and summarized in Table 2. from monoclinic to cubic. However, this type of phase change
10
was not observed when the increase in concentration of CsI
11
was equal to the decrease in concentration of PhNH3Br. On this
12
basis, it can be concluded that the strategy used in the second
13
set of experiments have shown promising geometrical changes.
14
In the final experiments, we have prepared (Cs)1(PhNH3)1PbBr3I1
15
perovskite with molar ratio of 1:1:1 for PhNH3Br:CsI:PbBr2 which
16
yields the orthorhombic phase (ICDD 01–072-7929).
17
The formation of the orthorhombic phase at equimolar
18
concentrations of CsI and PhNH3Br may suggest that the Cs +
19
ions predominantly enter the voids of PbBr3I forming the 3D
20
geometry. Based on the above p-XRD results, it can be
21
concluded that ratio of PhNH3Br and CsI used in the second set
22
of experiments show more promising geometrical changes as
23
compared to first set of experiments. Therefore, we used the
24
products of second set of experiments for further character-
25
ization. Due to high reactivity of salts, it was assumed that the
26
reaction in these set of experiments were complete and the
27 Figure 3. p-XRD patterns with increasing concentration of CsI and corre-
sponding decreasing the concentration of PhNH3Br with 2:0:1, 1.8:0.2:1, composition of the perovskite would be same as expected. To
28
1.6:0.4:1, 1.4:0.6:1, 1.2:0.8:1 and 1:1:1 molar ratios of PhNH3Br: CsI: PbBr2 in support this assumption, EDX analysis was also performed
29 (Cs)x(PhNH3)2-xPbBr4-xIx. which shows the composition with  5–6 % deviation as shown
30
in Table S1 (supporting information). These results were
31
repeated three times to ensure the reproducibility of results.
32 Table 2. Change of phase in (Cs)x(PhNH3)2-xPbBr4-xIx derivatives.
FTIR spectra as shown in Figure 4, confirm the presence of
33
Perovskite nanoparticles Concentration of A site cations Phase anilinium (organic cation) in the as-prepared derivatives of (Cs)x
34
35 (PhNH3)2PbBr4 X = 0.0 Layered
(Cs)0.1(PhNH3)1.9PbBr3.9I0.1 X = 0.1 Layered
36
(Cs)0.2(PhNH3)1.8PbBr3.8I0.2 X = 0.2 Layered
37 (Cs)0.3(PhNH3)1.7PbBr3.7I0.3 X = 0.3 Monoclinic
38 (Cs)0.4(PhNH3)1.6PbBr3.6I0.4 X = 0.4 Cubic
39 (Cs)0.6(PhNH3)1.4PbBr3.4I0.6 X = 0.6 Cubic
(Cs)0.8(PhNH3)1.2PbBr3.2I0.8 X = 0.8 Cubic
40
(Cs)1(PhNH3)1PbBr3I1 X = 1.0 Orthorhombic
41
42
43
44
It can be observed in the p-XRD patterns that when the
45
amount of CsI was increased by 10 to 20%, no significant
46
change was observed although the amount of PhNH3Br was
47
also reduced by 5 to 10% in (Cs)x(PhNH3)2-xPbBr4-xIx with 1.9/
48
1.8:0.1/0.2:1 molar ratio (PhNH3Br:CsI:PbBr2). However, some
49
new peaks start to appear. The concentration of CsI was then
50
increased to 30% while 15% of PhNH3Br was decreased, with
51
these concentrations, the (Cs)0.3(PhNH3)1.7PbBr3.7I0.3 derivative
52 Figure 4. FTIR spectrum of (Cs)x(PhNH3)2-xPbBr4-xIx derivatives.
having 1.7:0.3:1 molar ratio of PhNH3Br:CsI:PbBr2, showed the
53
monoclinic phase (ICDD: 00–018-0364).
54
However, the diffraction peaks of (PhNH3)2PbBr4 at 2q =
55
15.07, 21.32 and 30.34 have been merged in the (001), (010) (PhNH3)2-xPbBr4-xIx perovskites. The characteristic peaks at 3000–
56
and (002) planes of the monoclinic phase (Figure 3). The 3100 cm 1 indicate the vibration of sp2 hybridized C H group
57

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and at 1400–1700 cm 1 show the presence of C=C group of Figure 6 shows the photoluminescence (PL) emission spec-
1
benzene ring in 2D (PhNH3)2PbBr4 perovskite. However, the tra of the as-synthesized (Cs)x(PhNH3)2-xPbBr4-xIx derivatives with
2
intensity of these characteristic peaks decreases with increasing
3
concentration of CsI which confirms the successive decrease in
4
the concentration of PhNH3Br in (Cs)x(PhNH3)2-xPbBr4-xIx deriva-
5
tives. The decrease in intensity of ligand bands may be due to
6
the washing steps.
7
UV-Vis spectroscopy was performed on the nanoparticles of
8
(Cs)x(PhNH3)2-xPbBr4-xIx derivatives as presented in Figure 5. The
9
10
11
12
13
14
15
16
17
18
19
20
21 Figure 6. PL spectra of (Cs)x(PhNH3)2-xPbBr4-xIx perovskite derivatives with one
time increase concentration of CsI and corresponding 1=2 times decreasing
22
concentration of PhNH3Br in (Cs)x(PhNH3)2-xPbBr4-xIx.
23
24
25
an excitation wavelength of 333 nm. Complete PL spectra
26
within the range of 200–800 nm is presented in Figure S1
27
(supporting information). It can be observed that the as-
28 Figure 5. UV-Vis spectra of as-prepared (Cs)x(PhNH3)2-xPbBr4-xIx perovskite
derivatives with gradual increase in concentration of CsI and corresponding prepared perovskite nanoparticles show an emission peak at
29
decreasing concentration of PhNH3Br with 2:0:1, 1.8:0.2:1, 1.6:0.4:1, 1.4:0.6:1, 410 nm and 598 nm. The emission peak at 410 nm is the near
30
1.2:0.8:1 and 1:1:1 molar ratios of PhNH3Br: CsI: PbBr2 in (Cs)x(PhNH3)2-xPbBr4-x band edge peak. Whereas, the peaks at 333 nm and 666 nm are
31 Ix.
the 1st order and 2nd order excitation peaks.
32
The PL spectra shows that the all perovskite derivatives
33
have the principle peak at 598 nm, except, the sample x = 0.4
34
absorption spectra of pure (PhNH3)2PbBr4, showed absorption which shows a main peak at 598 nm along with a small
35
onset at about 315 nm, and as expected, the absorption onset shoulder peak at 530 nm, whereas the sample x = 0.6 nano-
36
is red shifted upon increasing the concentration of CsI during particles give a shoulder peak at 525 nm. The appearance of
37
the reaction. The sample with x = 1 shows the absorption onset the shoulder along with main peak suggests the formation of a
38
at 337 nm. This red shift in absorption spectra with increasing mixture of quasi-2D structures.
39
concentration of CsI is probably due to the conversion of the Similar behavior was also reported by Yuan et al. by using
40
2D geometry to 3D geometry. The absorption and emission organic cations.[18] The drop in intensity of PL peak was
41
results are summarized in Table 3. observed may be due to the formation of mixed dimensional
42
structures. In addition, all the derivatives of the as-prepared
43
perovskites show PL peak at same position regardless of
44 Table 3. Photoluminescence of as-prepared (Cs)x(PhNH3)2-xPbBr4-xIx deriva-
precursor composition which implies that the PL comes from
45 tives.
the quasi-2D crystals. Similar, PL results were also reported by
46 Organic/Inorganic Perovskite Nanoparticles labs. Onset (nm) lem. (nm) Byun et al.[11]
47 (Cs)x(PhNH3)2-xPbBr4-xIx
Transmission electron microscopy images of 2D (PhNH3)2
48
X = 0.0 315 598 PbBr4 perovskite nanoparticles show rectangular structures
49 X = 0.2 317 598 having dimensions of several hundred nanometers (Figure S2a
50 X = 0.4 327 598, 530
X = 0.6 329 598, 525
(supporting information)). In comparison, Figure S2b represents
51
X = 0.8 333 598 the images of perovskites with 20% CsI showing floppy sheets.
52
X = 1.0 337 598 Perovskites with 40% and 60% (X = 0.4, 0.6) CsI reveal plate-like
53
structures as shown in Figure S2c-d (supporting information).
54
TEM images of the sample with 80% CsI shows rectangular
55
nanosheets (Figure S2e (supporting information)). Interestingly,
56
when the concentration of CsI reaches to X = 1, island- like
57

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structures appeared as presented in Figure S2f (supporting Conflict of Interest
1
information). The folding in these sheets and weaker contrast
2
suggests their thin structures which are in agreement with The authors declare no conflict of interest.
3
previous reports[1a,16, 19]. The nanosheets are not separated, but
4
are stacked on each other which can be seen by varying Keywords: 2D Perovskite · Inorganic Perovskite · Organic-
5
contrast in the images. Inorganic perovski · Perovskite solar cell · Quasi-2D perovskite
6
Sichert et al.[1a] have reported the quasi spherical structures
7
of about 6 nm in size in conjugation with rectangular nano-
8
plates in background which in agreement with previous
9
studies. Similarly, in our studies, the same type of quasi
10
spherical 2D perovskite structures were also in conjugation [1] a) J. A. Sichert, Y. Tong, N. Mutz, M. Vollmer, S. Fischer, K. Z. Milowska, R.
11 Garca Cortadella, B. Nickel, C. Cardenas-Daw, J. K. Stolarczyk, Nano Lett.
with nanosheets of (Cs)0.4(PhNH3)1.6PbBr3.6I0.4 and (Cs)0.6(PhNH3)1.4
12 2015, 15, 6521–6527; b) M. A. Green, A. Ho-Baillie, H. J. Snaith, Nat.
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13
information). It was also observed that upon exposure to Hupp, M. G. Kanatzidis, J. Am. Chem. Soc. 2015, 137, 7843–7850.
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Experimental section contains detail synthetic methods, materi-
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JA thanks HEC, project no. 20-3020/R&D/HEC/14/654 for funds.
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NR is grateful for funding from the National Research Submitted: March 13, 2017
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Foundation (NRF), South Africa through the South African Revised: July 3, 2017
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Research Chair initiative (SARChI) Grant no. 64820. Accepted: July 6, 2017
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