Article

Cite This: J. Am. Chem. Soc. 2019, 141, 19099−19109 pubs.acs.org/JACS

Chemical and Structural Diversity of Hybrid Layered Double

Perovskite Halides
Lingling Mao,† Samuel M. L. Teicher,† Constantinos C. Stoumpos,‡ Rhys M. Kennard,†
Ryan A. DeCrescent,§ Guang Wu,∥ Jon A. Schuller,⊥ Michael L. Chabinyc,†
Anthony K. Cheetham,*,†,# and Ram Seshadri*,†,∥
†
Materials Research Laboratory and Materials Department, §Department of Physics, ∥Department of Chemistry and Biochemistry,
and ⊥Department of Electrical and Computer Engineering, University of California, Santa Barbara, California 93106, United States
‡
Department of Materials Science and Technology, University of Crete, Vassilika Voutes GR-700 13 Heraklion, Greece
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#
Department of Materials Science & Engineering, National University of Singapore 9 Engineering Drive 1, Singapore 117576,
Singapore
*
S Supporting Information
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ABSTRACT: Hybrid halide double perovskites are a class of

compounds attracting growing interest because of their richness
of structure and property. Two-dimensional (2D) derivatives of
hybrid double perovskites are formed by the incorporation of
organic spacer cations into three-dimensional (3D) double
perovskites. Here, we report a series of seven new layered
double perovskite halides with propylammonium (PA), octyl-
ammonium (OCA), and 1,4-butyldiammonium (BDA) cations.
The general formulas of the compounds are AmMIMIIIX8
(single-layered Ruddlesden−Popper type with m = 4 and A =
PA or OCA, and single-layered Dion−Jacobson type with m =
2 and A = BDA, MI = Ag, MIII= In or Bi, X = Cl or Br) and
PA2CsMIMIIIBr7 (bilayered, with MI = Ag, MIII = In or Bi).
These families of compounds demonstrate great versatility, with tunable layer thickness, the ability to vary the interlayer spacing,
and the ability to selectively tune the band gap by varying the MI and MIII cations along with the halide anions. The band gap of
the single-layered materials varies from 2.41 eV for PA4AgBiBr8 to 3.96 eV for PA4AgInCl8. Photoluminescent emission spectra
of the layered double perovskites at low-temperature (100 K) are reported, and density functional theory electronic structure
calculations are presented to understand the nature of the band gap evolution. The development of new structural and
compositions in layered double perovskite halides enhances the understanding of structure−property relations in this important
family.

■ INTRODUCTION
Hybrid organic−inorganic halide perovskite materials have
ally linked octahedra have demonstrated interesting physical
properties and desirable “lead-free” compositions,27 which
sparked widespread interest due to the richness of their make them a unique class of hybrid materials. Vacancy-ordered
optoelectronic properties.1−5 The three-dimensional (3D) double perovskites28,29 can also be formed with a 4+ metal
halide perovskites are established materials that show high alternating with a vacancy as in Cs2SnI6.30
power conversion efficiencies in solar cells6,7 and high external By tuning the size and nature of the A cation (or
quantum efficiencies in light-emitting diodes.8−11 The general combinations of cations) in 3D AMX3 perovskites, distinct
formula of the 3D hybrid halide perovskites is AMX3, where A classes of hybrid 2D layered perovskites can be obtained,
is a small organic cation such as methylammonium (MA+), including the so-called Ruddlesden−Popper (RP) series31,32
formamidinium (FA+); M is Ge2+, Sn2+, or Pb2+, and X is a and the Dion−Jacobson (DJ) series33,34 (displayed in Figure
halide.12 Double perovskites are obtained by doubling the 1). In a similar vein, the introduction of appropriate large
formula, using alternating 1+ and 3+ on the M site instead of a organic spacing cations35 has recently yielded hybrid layered
2+ cation metals. The resulting 3D structures have the general double perovskite halides (schematically represented in Figure
formula A2MIMIIIX613 (displayed in Figure 1). While the A site 1). The first example was obtained by incorporating butyl-
cation stems from a similar pool as found in AMX3 perovskites, ammonium (BA) cations into Cs2AgBiBr6 resulting in two new
MI and MIII offer a wide range of tunability, from Na+, K+, Cu+,
Ag+, Au+, for MI and, from Y3+, Gd3+, Au3+, In3+, Tl3+, Sb3+, Received: September 14, 2019
Bi3+, for MIII.14−26 Double perovskites with three-dimension- Published: November 7, 2019

© 2019 American Chemical Society 19099 DOI: 10.1021/jacs.9b09945

J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Figure 1. Schematic illustration of the evolution of the 3D perovskite structure to 2D layered double perovskites. For clarity, the A cations are not
depicted. Cation ordering in the M site of AMX3 perovskite yields the 3D double perovskite structure, and the insertion of spacer cations allows the
layering. The two main classes of layered structures are the Ruddlesden−Popper type, depicted on the left as the n = 2 member, and the Dion−
Jacobson type, shown on the right as the n = 1 member. A few sample organic spacer cations are depicted in the inset.

structures, BA4AgBiBr8 and BA2CsAgBiBr7.36 High-pressure the desired crystals upon addition of the bulky alkylammonium
studies based on BA4AgBiBr837 and using BA2CsAgBiBr738 for cation. All as-formed crystals have a signature plate-like
X-ray detection have just been reported. An iodide-based 2D morphology with varying color, as seen in Figure 2a−e. The
double perovskite [AE2T]2AgBiI8 (AE2T = 5,5′-diylbis-
(amino-ethyl)-[2,2′-bithiophene]) has also been recently
reported, with an optical band gap of 2.00 eV.39 The
hydrothermal synthesis and structure of the compounds
(C 6 H 16 N 2 ) 2 AgBiI 8 ·H 2 O and (C 6 H 16 N 2 ) 2 CuBiI 8 ·0.5H 2 O
[C6H14N2 = 1,4-cyclohexane-diamine] have also been reported
recently.40
With the aim of evaluating the chemical and structural
versatility of hybrid layered double perovskite halides, and to
gain insight into structure−property relations, we demonstrate
that a large family of cation-ordered hybrid double-perovskite
halides can be obtained through the judicious selection of a
range of organic and M cations and halide anions. New
members of hybrid cation-ordered RP and DJ phases are
reported. First we describe the successful preparation of 2D
derivatives PA4AgInCl8 and PA4AgBiBr8 where PA = propyl- Figure 2. Optical microscope images of (a) PA4AgInCl8, (b)
PA4AgInBr8(colorless, the purple comes from interference effect),
ammonium. These could be thought of as being derived from (c) PA4AgBiBr8, (d) PA2CsAgBiBr7, and (e) PA2CsAgBi0.5Br7. (f)
the known 3D double perovskites Cs2AgInCl6 and Cs2AgBiBr6. Selected Area Electron Diffraction (SAED) of fragments of
Alternatively, these could be seen as being derived from the n = PA4AgBiBr8, showing spots corresponding to the labeled d-spacings,
1 RP phase PA2PbX4, with Pb2+ being replaced by alternating with real-space Transmission Electron Microscopy (TEM) image of
Ag+ and In3+/Bi3+ To our surprise, although Cs2AgInBr6 has fragments inset. Scale bars: 2 nm−1 for the SAED image and 1 μm for
not been reported and does not seem to form directly through the real-space image. Inset shows d-spacing of 3.1 Å.
solution methods, the layered product PA4AgInBr8 does form
and is structurally analogous to PA4AgBiBr8. The single-layered
(n = 1) series is further expanded by using the longer general principle remains similar to the one used for common
octylammonium (OCA) cation, forming OCA4AgBiBr8. The 2D perovskites, although due to the relatively lower solubility
use of a dication, 1,4-butanediammonium (BDA) yields the n of the material, unique processes are required, such as the
= 1 DJ phase BDA2AgBiBr8. Building up the layer thickness is filtration of some insoluble precipitates to afford clear solutions
realized up to n = 2, with the successful preparation of that allow for the isolation of compositionally pure compounds
PA2CsAgBiBr7 andPA2CsAgIn0.5Bi0.5Br7. The optical proper- (for more details see Methods). Direct visualization of the
ties are highly tunable, through varying the layer thickness, structure of a PA4AgBiBr8 crystal was obtained via transmission
increasing the length of the organic spacer, changing the halide electron microscopy (TEM) and selected area electron
(from Cl− to Br−), and alloying the metal (MIII). With the diffraction (SAED) (Figure 2f), whereby analysis was
flexible toolbox described above, we have discovered seven performed on thin edges of fragments of single-layered crystals.
new hybrid layered double perovskite halides with tunable The fragments were deposited onto TEM grids by crushing the
properties. crystals onto TEM grids with a razor blade, resulting in

■
crystallites of different orientations being simultaneously
imaged (for imaging conditions, see Methods section). An
RESULTS AND DISCUSSION example of selected area electron diffraction analysis on such a
Synthesis. The synthesis of the 2D double perovskites fragment is shown in Figure 2f, with the real space image of a
involves the dissolution of the metal precursors in concen- selected area shown in the inset. The fragments are primarily
trated hydrohalic acid media followed by the precipitation of oriented along the [100] zone axis, as evidenced by strong
19100 DOI: 10.1021/jacs.9b09945
J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Figure 3. Crystal structures of the single-layered compounds (a) PA4AgInCl8, (b) PA4AgInBr8, (c) PA4AgBiBr8, (d) BDA4AgBiBr8, and (e)
OCA4AgBiBr8. Hydrogens are omitted for clarity.

Table 1. Crystal Data and Structure Refinement for PA4AgInCl8, PA4AgInBr8, and PA4AgBiBr8 at 293 K
PA4AgInCl8a PA4AgInBr8b PA4AgBiBr8c
empirical formula (CH3(CH2)2NH3)4AgInCl8 (CH3(CH2)2NH3)4AgInBr8 (CH3(CH2)2NH3)4AgBiBr8
crystal system triclinic monoclinic monoclinic
space group P1 C2/m C2/m
unit cell dimensions a = 7.454(3) Å, α = 90.141(10)° a = 24.5633(13) Å, a = 24.503(7) Å,
b = 7.866(3) Å, β = 89.992(10)° b = 7.7838(4) Å, b = 7.964(2) Å,
c = 24.629(8) Å, γ = 90.049(11)° c = 8.2501(4) Å, c = 8.384(2) Å,
β = 90.091(2)° β = 90.045(9)°
volume 1444.0(8) Å3 1577.38(14) Å3 1636.0(8) Å3
Z 2 2 2
density (calcd) 1.717 g/cm3 2.321 g/cm3 2.429 g/cm3
absorption coefficient 2.224 mm−1 11.491 mm−1 15.746 mm−1
F(000) 744 1032 1100
θ range for data collection 0.827−27.763° 2.47−31.74° 1.662−26.467°
index ranges −9 ≤ h ≤ 8, −36 ≤ h ≤ 36, −30 ≤ h ≤ 30,
−8 ≤ k ≤ 9, −11 ≤ k ≤ 11, −8 ≤ k ≤ 9,
−31 ≤ l ≤ 31 −12 ≤ l ≤ 12 −10 ≤ l ≤ 8
reflections collected 9706 41 147 5285
independent reflections 5690 [Rint = 0.0442] 2845 [Rint = 0.0376] 1769 [Rint = 0.0568]
completeness to θ = 24.868° 98.70% 100% 97.20%
refinement method full-matrix least-squares on F2
data/restraints/parameters 5690/0/157 2845/10/54 1769/10/53
final R indices [I > 2σ(I)] Robs = 0.0760, wRobs = 0.1955 Robs = 0.0496, wRobs = 0.1457 Robs = 0.0956, wRobs = 0.2648
R indices [all data] Rall = 0.1952, wRall = 0.2637 Rall = 0.0661, wRall = 0.1472 Rall = 0.1381, wRall = 0.2787
largest diff. peak and hole 1.484 and −1.773 e·Å−3 3.06 and −1.30 e·Å−3 1.581 and −1.705 e·Å−3
a
R = ∑||Fo| − |Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |Fc|2)2]/∑[w(|Fo|4)]}1/2 and w = 1/[σ2(Fo2) + (0.1245P)2], where P = (Fo2+2Fc2)/3. bR = ∑||Fo| − |
Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |Fc|2)2]/∑[w(|Fo|4)]}1/2 and w = 1/[σ2(Fo2) + (0.1025P)2 + 20.8371P], where P = (Fo2 + 2Fc2)/3. cR = ∑||Fo| − |
Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |Fc|2)2]/∑[w(|Fo|4)]}1/2 and w = 1/[σ2(Fo2) + (0.0843P)2 + 136.0832P], where P = (Fo2 + 2Fc2)/3.

diffraction from (200), (400), and (600) d-spacings (in layered perovskites.4,41 We started with a short alkyl-
yellow) with some contribution from the [133] and [143] ammonium cation, propylammonium (PA) as the template
zone axes. and then continued to expand to octylammonium (OCA) and
Crystal Structures. The general structures of these layered the dication 1,4-butanediammonium (BDA). Variations on the
double perovskites are similar to the traditional layered MIII and X parts have been carried out: In and Bi for MIII, and
perovskite, with the distinct difference that the metal-centered Cl and Br for the halide, as seen in Figure 1. Efforts have also
octahedra are made from alternating MI and MIII (MI = Ag, been made to synthesize higher layer thicknesses; however, we
MIII = In, Bi). The layered double perovskites have general were successful only up to two layers. Detailed crystallographic
formulas of AmMIMIIIX8 and PA2CsMIMIIIBr7. The alternating data and refinement details are listed in Tables 1 and 2.
metal arrangement of the single-layered materials studied here Propylammonium cations were used to separate the 3D
is illustrated in Figure 3, where the layers are composed of parent structure of Cs2AgInCl6 and form the RP-type layered
corner-sharing Ag/In-centered (blue/pink) and Ag/Bi-cen- perovskite, PA4AgInCl8, as shown in Figure 3a. PA4AgInCl8
tered (blue/yellow) octahedra. The layers follow the (100)- crystallizes in the triclinic space group p. AgI and InIII occupy
orientation, which is the most common type found in the distinct metal sites, which can be clearly distinguished by the
19101 DOI: 10.1021/jacs.9b09945
J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Table 2. Crystal Data and Structure Refinement for BDA2AgBiBr8 OCA4AgBiBr8, PA2CsAgBiBr7, and PA2CsAgIn0.5Bi0.5Br7 at
293 K
BDA2AgBiBr8a OCA4AgBiBr8b PA2CsAgBiBr7c PA2CsAgIn0.5Bi0.5Br74
empirical formula (NH3(CH2)4NH3)2AgBiBr8 (CH3(CH2)7NH3)4AgBiBr8 (CH3(CH2)2NH3)2CsAgBiBr7 (CH3(CH2)2NH3)2CsAgIn0.48Bi0.52Br7
crystal system triclinic monoclinic monoclinic monoclinic
space group P1 P2/m P21/m P21/m
unit cell dimensions a = 8.1018(3) Å, a = 8.2024(7) Å, a = 8.053(4) Å, a = 8.008(10) Å,
α = 101.1960(10)° b = 8.1797(6) Å, b = 7.997(3) Å, b = 7.877(9) Å,
b = 8.2433(3) Å, c = 21.1217(18) Å, c = 18.536(8) Å, c = 18.310(2) Å,
β = 92.055(2)° β = 101.195(3)° β = 102.503(11)° β = 102.60(3)°
c = 9.6813(4) Å,
γ = 90.3960(10)°
volume 633.79(4) Å3 1390.2(2) Å3 1165.5(9) Å3 1127(2) Å3
Z 1 1 2 2
density (calcd) 2.978 g/cm3 1.764 g/cm3 3.218 g/cm3 3.194 g/cm3
absorption coefficient 20.314 mm−1 9.284 mm−1 21.907 mm−1 19.398 mm−1
F(000) 514 710 1000 967
θ range for data 2.516−30.594° 2.490−26.660° 1.125−25.678° 2.279−24.868°
collection
index ranges −11 ≤ h ≤ 11, −11 ≤ h ≤ 11, −9 ≤ h ≤ 4, −9 ≤ h ≤ 9,
−11 ≤ k ≤ 11, −11 ≤ k ≤ 11, −9 ≤ k ≤ 9, −7 ≤ k ≤ 9,
−13 ≤ l ≤ 13 −26 ≤ l ≤ 26 −20 ≤ l ≤ 22 −19 ≤ l ≤ 21
reflections collected 20 023 40 227 4810 4216
independent 3872 [Rint = 0.0555] 2702 [Rint = 0.0694] 2138 [Rint = 0.1009] 2092 [Rint = 0.0740]
reflections
completeness to 99.40% 85.50% 92.40% 98.40%
θ = 24.868°
refinement method full-matrix least-squares on F2
data/restraints/ 3872/0/105 2702/31/69 2138/13/78 2092/13/78
parameters
final R indices Robs = 0.0421, Robs = 0.0919, Robs = 0.1304, Robs = 0.1313,
[I > 2σ(I)] wRobs = 0.1140 wRobs = 0.2714 wRobs = 0.2742 wRobs = 0.2580
R indices [all data] Rall = 0.0445, Rall = 0.1223, Rall = 0.2065, Rall = 0.1908,
wRall = 0.1162 wRall = 0.2752 wRall = 0.3171 wRall = 0.2801
largest diff. peak and 4.539 and −2.316 e·Å−3 2.93 and −1.48 e·Å−3 5.786 and −4.368 e·Å−3 3.276 and −4.440 e·Å−3
hole
a
R = ∑||Fo| − |Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |Fc|2)2]/∑[w(|Fo|4)]}1/2, and w = 1/[σ2(Fo2) + (0.0661P)2 + 2.3572P], where P = (Fo2 + 2Fc2)/3. bR
= ∑||Fo| − |Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |Fc|2)2] /∑[w(|Fo|4)]}1/2, and w = 1/(σ2(I) + 0.0004I2). cR = ∑||Fo| − |Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |
Fc|2)2]/∑[w(|Fo|4)]}1/2, and w = 1/[σ2(Fo2) + (0.0001P)2 + 373.8861P], where P = (Fo2 + 2Fc2)/3. 4R = ∑||Fo| − |Fc||/∑|Fo|, wR = {∑[w(|Fo|2 − |
Fc|2)2]/∑[w(|Fo|4)]}1/2, and w = 1/[σ2(Fo2) + 231.5294P], where P = (Fo2 + 2Fc2)/3.

octahedral environments. The In−Cl bond lengths (2.50 and seen in Figure 4h, where the strongest H-bonds are between
2.53 Å) are much shorter and more uniform compared with nitrogen and the terminal Br (3.31 and 3.35 Å). With the same
the Ag−Cl bonds (2.48 and 2.93 Å) in Figure 4d. Compared organic spacing cation PA, the difference in the M−X−Ag
to the uniform Ag−Cl bond length in the 3D Cs2AgInCl6 angles (M = In3+, Bi3+, X = Cl, Br) are quite small, 164.8°,
structure (2.73 Å), the 2D material show a large deviation of 164.1°, and 163.8°, respectively.
the equatorial (2.93 Å) and axial (2.48 Å) Ag−Cl bond Changing MIII from In to Bi, PA4AgBiBr8 crystallizes in the
lengths. The two short axial bonds are situated in the positions monoclinic space group C2/m, which is expected to be the
without In connections (perpendicular to the layers). The same as the previously reported structure BA4AgBiBr8 (BA =
extensive hydrogen-bonding network between the NH3+ group butylammonium).36 Similar to the PA4AgInCl8 case, the AgI
and Cl is illustrated in Figure 4g, where the cutoff of the N···Cl and BiIII sites are clearly identifiable, and the AgI site still
distance is 3.45 Å. Among the hydrogen bonds (∼3.40 Å),42 undergoes distortion because of the compression of the axial
those between nitrogen and terminal Cl are the strongest (3.18 Ag−Br bonds (2.65 Å vs 3.00 Å). The BiIII site remains rather
and 3.20 Å, Figure 4g). undistorted, as all the Bi−Br bond lengths are ∼2.82 Å and the
The bromide analogue PA4AgInBr8 crystallizes in the Br−Bi−Br angles are ∼90° (Figure 4f). Only one kind of
monoclinic space group C2/m. The Ag and In sites are fully hydrogen bond is observed in the structure, which is between
resolved, unlike the recently reported structure [AE2T]2AgBiI8 N and the terminal Br on Bi. The donor−acceptor distance is
(AE2T = 5,5′-diylbis(aminoethyl)-[2,2′-bithiophene]), where 3.15 Å (Figure 4i). This particularly short H-bond could be
Bi and Ag, as well as the bridging iodine, have site disorders.39 explained by the more electron-positive nature of Bi (than In),
The In−Br bonds have consistent lengths of 2.66 and 2.67 Å, which leads to a stronger interaction between the Br on Bi and
whereas the [AgBr6]5− octahedron still again has compressed H rather than the Br on In.
octahedral geometry, with elongated equatorial Ag−Br bonds The single-layered hybrid double perovskites can be
(3.07 Å) and short axial Ag−Br bonds (2.59 Å) (Figure 4e). expanded by changing the organic cations. Short and long,
The H-bonds are even weaker than in the Ag/Br system, as singly and doubly protonated cations such as dibutyl-
19102 DOI: 10.1021/jacs.9b09945
J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Figure 4. Top-down view of the layers in (a) PA4AgInCl8, (b) PA4AgInBr8, and (c) PA4AgBiBr8. Local bonding environment of (d) PA4AgInCl8,
(e) PA4AgInBr8, and (f) PA4AgBiBr8. Hydrogen-bonding network of (g) PA4AgInCl8 (H-bond cutoff 3.45 Å), (h) PA4AgInBr8 (H-bond cutoff 3.50
Å), and (i) PA4AgBiBr8 (H-bond cutoff 3.50 Å).

ammonium (BDA) and octylammonium (OCA) have been in the RP phase the layers are shifted by (1/2, 0) (Figure 5c).
successfully demonstrated in the Ag−Bi−Br system, where the The local octahedral environments of AgI and BiIII are rather
interlayer distance varies from 9.49 to 20.72 Å, shown in similar to PA4AgBiBr8, as seen in Figure 5b,d. One major
Figure 1d,e. BDA2AgBiBr8 belongs to the DJ type33,43 layered difference in the layered double perovskite system compared
perovskites, where one spacing cation instead of two is in the with the Pb or Sn based layered perovskite system is that the
interlayer space (Figure 2d). A distinct difference between the metal-halide-metal (M−X−M) angles are not much involved in
DJ and RP phases comes from the layer orientation, where in affecting the optical properties.33,44 However, substantial
the DJ phase the layers lie on top of each other (Figure 5a) and change in the MI−X−MIII is identified, where the smallest
Ag−Br−Bi angle, 157.3°, is seen in the BDA case. The angle
increases to 163.8° in the PA structure, and increases further to
169.5° for the longest ammonium here, OCA (Figure 5b,d).
The much smaller interlayer distance in the DJ phase (9.49 Å)
compared to the RP phase utilizing a long chain ammonium
cation (20.72 Å) could potentially facilitate charge transfer
between the inorganic layers like in the Pb-based systems.31,33
The double-layered structures, PA 2 CsAgBiBr 7 and
PA2CsAgIn0.5Bi0.5Br7, both crystallize in the monoclinic space
group P21/m, as does the BA analogue.36 The crystallographic
refinement details are given in Table 2. The Cs+ cations occupy
the empty cavities in the inorganic cages, while the organic
cations lie between the double layers. Alloying In and Bi in a
1:1 ratio is accomplished, with a refined occupancy of In
(0.48) and Bi (0.52). We have synthesized a small amount of
PA2CsAgInBr7; however, the poor quality of the crystals
prohibits us from performing structural determination and
further characterizations. Noticeable changes in the inorganic
framework are shown in Figure 5c,d, where the Bi−Br−Bi
angles decrease from 172.9° and 179.1° to 165.2° and 167.9°,
Figure 5. Crystal structures of BDA2AgBiBr8 and OCA4AgBiBr8. (a, which is reasonable when alloying a much smaller metal cation
c) Top-down views of the layer orientation. (b, d) Local coordination (In) into the system. The alloying also causes shrinkage in the
environments for Ag and Bi for BDA2AgBiBr8 and OCA4AgBiBr8, unit cell, the most pronounced change seen in c (from 18.536
respectively. Hydrogens are omitted for clarity. (8) Å to 18.310 (2) Å).
19103 DOI: 10.1021/jacs.9b09945
J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Optical Properties. In accordance with the parent 3D

structure Cs2AgBiBr6, which has an indirect band gap, the 2D
derivatives have similar absorption features, with slightly higher
energy edge onsets corresponding to their lighter colors
(Figure 2a−e). The absorption spectra of PA4AgBiBr8,
PA2CsAgBiBr7, the butylammonium (BA) analogues, and the
3D double perovskite Cs2AgBiBr6 are shown in Figure 6a for

Figure 7. Optical absorption spectra of (a) PA 4 AgBiBr 8 ,

PA2CsAgBiBr7 with the BA analogues, and the 3D double perovskite
Cs2AgBiBr6. (b) PA4AgInBr8, PA4AgInCl8, and their BA analogues for
comparison. (c) Changing the organic spacers in the Ag−Bi−Br
single-layered system. (d) PA2CsAgBiBr7 and PA2CsAgIn0.5Bi0.5Br7.

Figure 6. Crystal structures of the two-layered compounds (a)

PA2CsAgBiBr7 and (b) PA2CsAgIn0.5Bi0.5Br7. (c, d) Inorganic
framework of the basic building unit and the M−Br−M angles of
PA2CsAgBiBr7 and PA2CsAgIn0.5Bi0.5Br7. Hydrogens are omitted for
clarity.

comparison. The single- and double-layered members of PA

and BA have similar band gaps of 2.41 and 2.32 eV,
respectively (Figure 6a). The band gap of Cs2AgBiBr6
measured by diffuse reflectance is 2.20 eV, similar to the
previously reported value (2.19 eV).17 For the rest of the
single-layered members with different organic spacers,
BDA2AgBiBr8 and OCA4AgBiBr8 have similar band gaps of
2.43 and 2.45 eV compared to PA4AgBiBr8(2.41 eV) (Figure
7c), indicating that the effect of the organic spacers upon the
magnitude of the optical gap is minimal. In Pb- or Sn- based
layered systems, the organic cations effectively affect the band
gap by impacting the respective M−X−M angles.33,44 For
PA4AgInBr8, a sharp absorption edge of 3.15 eV is estimated as
Figure 8. Steady-state photoluminescence (PL) spectra at 100 K for
the band gap of this material. The BA analogue has an (a) PA4AgInBr8, PA4AgSb0.5Bi0.5Br8, and PA4AgIn0.5Bi0.5Br8. (b)
absorption edge at higher energy of 3.32 eV (Figure 7b). The Temperature-dependent PL for PA4AgSb0.5In0.5Br8 from 100 to 293
direct band gap 3D double perovskite Cs2AgInCl6 has a K.
reported band gap of 3.23 eV.22 The 2D derivative compounds
PA4AgInCl8 and BA4AgInCl8 have a larger band gaps of 3.96 validation under more extreme experimental conditions (e.g.,
eV. In contrast to the Pb- and Sn-based 2D systems, excitonic lower temperature or under pressure). The PL emission peaks
absorption features associated with the 2D confinement are of PA4AgInBr8, PA4AgSb0.5Bi0.5Br8, and PA4AgIn0.5Bi0.5Br8
not clearly observed in the layered double perovskites emit across the range of 449−705 nm at 100 K, exhibiting a
measured by diffuse reflectance spectra. This observation is wide range of tunability. Detailed PL emission energies and the
similar to the previously reported layered double perovskites, corresponding band gaps are given in Table 3. Temperature-
where the low-energy absorptions are relatively broad dependent PL data were collected for PA4AgSb0.5Bi0.5Br8 (as it
compared to the Pb-based systems.39 Alloying Bi and In in emits brighter) and the PL gradually quenches with increasing
PA2CsAgBiBr7 increases the band gap slightly as seen in Figure temperature to room temperature (Figure 8b). The PL
7d, from 2.32 to 2.35 eV. emission center and bandwidth remain unchanged. The
Weak photoluminescence (PL) is observed in the 2D generally broad PLs, especially with the Bi/Sb and Bi/In
layered double perovskite system (Figure 8), with most of the solid solutions, are similar to those observed in the A3M2I9
PL are only observable at low temperatures. The PL for systems (A = Rb, Cs; M = Sb, Bi). This could be due to self-
pristine PA4AgBiBr8 is too weak, which needs further trapped excitons (STEs) arising from electron−phonon
19104 DOI: 10.1021/jacs.9b09945
J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Table 3. Summary of Band Gaps and PL Emission Energies band gap results from a combination of Ag d and X p states.
of Selected Compounds Right at the VBM in the Bi3+ compounds, there is a small lone-
pair contribution from Bi s orbitals as in other similar halide
Eg (eV) PL (eV)
perovskite-related materials. Bi s and Ag s contributions are
PA4AgBiBr8 2.41 NA plotted in Figure S6.
PA4AgSb0.5Bi0.5Br8 2.51 1.93 With the aim of obtaining better quantitative matching with
PA4AgIn0.5Bi0.5Br8 2.56 1.76 our experimental results, we also compared our results with
PA4AgInBr8 3.15 2.76 calculations using the HSE06 functional, which is known to
PA4AgInCl8 3.96 NA
improve band gap estimation across a wide population of
*Cs2AgBiBr6 2.20 1.91
semiconductors.48 The HSE06 band gaps are much closer to
the experimentally determined values for all our materials.
coupling.45,46 The large Stokes shifts of PA4AgSb0.5Bi0.5Br8 and However, there is a significant discrepancy between the
PA4AgIn0.5Bi0.5Br8 are possibly originated from STEs, as calculated and measured band gaps of PA4AgInBr8 even with
previously seen in (tms)4Pb3Br10 (tms = trimethylsulfonium), HSE06 (Table S4).
which has a layered structure with large Stokes shift and broad Connor and co-workers considered the related systems,
PL emission.47 BA2CsAgBiBr7 and BA4AgBiBr8, concluding based on first-
Band Structure Calculations. To complement our principles calculations on those systems, as well as related,
experimental results, we performed first-principles simulations layered systems, that there should be an indirect to direct band
in order to understand the influence of these new structures gap transition with reduction in the layer parameter, n.36 We
and compositions on the electronic transitions. The band find that none of our RP prototype structures have true direct
structures in Figure 9 summarize our major findings. Overall, band gaps, although BA4AgBiBr8 has valley degeneracy
these calculations qualitatively match our experimental resulting in equal indirect and direct gaps. Given the chemical
findings: the band gap of the single-layered compound similarity between the DJ phase BDA2AgBiBr8which has a
PA4AgBiBr8 is smaller than the corresponding two-layered low-dispersion conduction band with the smallest direct band
compound, PA2CsAgBiBr7, and the band gap of the chloride, gap transitionand the other structures considered, the
PA4AgInCl8, exceeds that of the corresponding bromide, structure archetype (DJ/RP) may be even more important
PA4AgInBr8. We performed calculations with and without the than the layering for the direct/indirect transition in this
inclusion of spin−orbit coupling (SOC) effects and found that system.
SOC has a significant impact on the band gap in compounds As a final note, we want to caution against strong statements
containing Bi3+, which have significant Bi p character in the about the location of the conduction band maxima and minima
conduction band. SOC has little effect on the band gap of of the calculated band gaps in materials with exceptionally flat
compounds containing the InIII ion, which have predominant conduction bands such as PA2CsAgBiBr7, PA4AgBiBr8, and
In s character in the conduction band. In addition to the BDA2AgBiBr8. Due to computational expense, simulations are
greater mass of Bi, which increases the magnitude of the SOC, frequently performed on idealized structures in which organic
the lack of orbital angular momentum in the In s (l = 0) state cations are replaced with ions such as Cs+, or by using only a
greatly reduces the impact of SOC on the conduction band in single functional. For these flat band compounds, we find that
the In compounds. A good understanding of the conduction both explicit inclusion of the organic spacer and the choice of
band character and the influence of SOC can therefore be functional can change the location of the conduction band
gained by simply considering the orbital filling of the MIII minimum within the Brillouin zone, although the dispersion for
cations. The predominant character of the bands below the the bands is largely qualitatively unchanged. Brillouin zone

Figure 9. DFT PBE band structure calculations for PA2CsAgBiBr7, PA4AgBiBr8, PA4AgInBr8, PA4AgInCl8, and BDA2AgBiBr8 from left to right.
Orbital projections are represented as circles with sizes corresponding to relative contributions. The conduction and valence bands calculated using
the HSE06 functional are additionally overlaid.

19105 DOI: 10.1021/jacs.9b09945

J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

locations and values of all calculated band gaps are available in stirring at 122 °C for 10 min until the solution turned clear. Orange
Tables S1−S3. crystals (Cs2AgBiBr6, 3D phase) precipitated during slow-cooling to

■
room temperature. Clear solution was obtained after filtering out the
CONCLUSIONS undesired orange 3D phase, and another 160 mg of propylamine was
added before heating and stirring at 122 °C until the solution turned
In conclusion, we have designed and synthesized seven new clear. The same process was repeated again, but ultimately no more
hybrid layered cation-ordered perovskite halides with different orange phase was formed and yellow plate-like crystals precipitated
structures and compositions. Unlike conventional Pb-based 2D during slow-cooling to room temperature. Yield 365 mg (30.5% based
systems, the excitonic features are less visible and, so far, on total Bi content). PA2CsAgIn0.5Bi0.5Br7 was synthesized by
appear to possess limited ability to be built into higher (than n dissolving 166.9 mg (1 mmol) of silver acetate, 212.8 mg (1 mmol)
= 2) layer numbers using solution methods. These compounds of CsBr, 233 mg (0.5 mmol) of Bi2O3, and 110.6 mg of InCl3(0.5
mmol) in 6 mL of HBr. To the above solution was added 160 mg of
are promising in the sense that (i) a wide range of organic
propylamine, and stirring continued at 122 °C for 10 min until the
spacing cations can be used (here PA, BA, BDA, and OCA); solution turned clear. An orange phase of Cs2AgBiBr6 and an
(ii) tunable layer thickness can be achieved, (iii) a metal unknown light-yellow phase precipitated during slow-cooling to room
alloying strategy on both 1+ and 3+ sites can be carried out; temperature. By filtering the above solution, the mother solution was
and (iv) varying the halide can be used to control the kept undisturbed for 1−2 days and yellow plate-like crystals formed.
optoelectronic properties. We have showcased some of our Only a small amount of PA2CsAgIn0.5Bi0.5Br7 was obtained, enough
successful syntheses with detailed structural analysis of these for single-crystal diffraction and optical absorption measurement.
new materials and optical characterization. The realization of Single-Crystal X-ray Diffraction. Full-sphere data were collected
these new structures further enlarges the scope of layered using a Bruker KAPPA APEX II diffractometer equipped with an
double perovskite halides and points to the possibility of APEX II CCD detector using a TRIUMPH monochromator with Mo
Kα source (λ = 0.71073 Å) with MX Optics or a Bruker D8
synthesizing a huge range of accessible materials with VENTURE diffractometer equipped with a Kappa goniometer stage, a
interesting and tunable optoelectronic properties.

■
PHOTON II CPAD detector, and an IμS 3.0 Mo Kα source (λ =
0.71073 Å). Data were collected at 293 K. The collected data were
METHODS integrated and applied with multiscan absorption correction using the
Materials. InCl3 (98%), Sb2O3 (99%), silver acetate (99%), APEX2 or APEX3 software. Crystal structures were solved by direct
propylamine (98%), butylamine (99.5%), 1,4-diaminobutane (99%), methods (full-matrix least-squares on F2) and refined by full-matrix
octylamine (99%), hydrochloric acid (semiconductor grade, 37%), least-squares on F2 using the OLEX2 program package49 and by
and hydrobromic acid (ACS reagent, 48%) were purchased from charge flipping (full-matrix least-squares on F2) using the Jana2006
Sigma-Aldrich and used as received. Bi2O3 (99.9%) and CsBr (99%) package.
were purchased from Alfa Aesar and used as received. Transmission Electron Microscopy (TEM). Transmission
Synthesis of PA4AgInCl8. First, 333.8 mg (2 mmol) of silver acetate electron microscopy (TEM) and selected area electron diffraction
and 442.4 mg (2 mmol) of InCl3 were dissolved in 6 mL of HCl. (SAED) images were acquired using an FEI Tecnai G2 Sphera
Next, 1 mL of propylamine was added to the previous solution before operating at 200 keV in bright field mode. n = 1 PA4AgBiBr8 crystals
heating and stirring at 108 °C. After heating and stirring for 5−10 were crushed onto TEM grids (Ted Pella No. 01824, ultrathin C film
min, white precipitates formed. A clear solution was obtained after the on holey carbon support film, 400 mesh, Cu) using a razor blade.
white precipitates were filtered out, which was heated and stirred for Prior to crushing, the n = 1 PA4AgBiBr8 crystals were rinsed with
another 10 min at 108 °C. Colorless plate-like crystals precipitated ether to remove residual HI. With intention to reduce beam damage
during slow-cooling to room temperature. Yield 125 mg (8.4% based and obtain diffraction patterns of the smallest area possible, a spot size
on total In content). The low yield of PA4AgInCl8 is primarily due to of (5) was selected for both real-space and SAED imaging. The scale
several filtrations during the synthesis to exclude AgCl precipitate, for both the SAED and real-space images was calibrated using Au
which filter most of the starting materials out. An analogous nanoparticles. An objective aperture was not employed for imaging.
procedure was used to synthesize BA4AgInCl8 for comparison of Optical Absorption Spectroscopy. Optical diffuse reflectance
the band gap. measurements were performed using a Shimadzu UV-3600 UV−vis−
Synthesis of PA4AgInBr8. First, 166.9 mg (1 mmol) of silver acetate NIR spectrometer operating in the 220−1000 nm region using BaSO4
and 221.2 mg (1 mmol) of InCl3 were dissolved in 5 mL of HBr. as the reference of 100% reflectance. The band gap of the material was
Next, 0.5 mL of propylamine was added to the previous solution estimated by converting reflectance to absorption according to the
before heating and stirring at 122 °C for 10 min until the solution Kubelka−Munk equation: α/S = (1 − R)2(2R)−1, where R is the
turned clear. Colorless plate-like crystals precipitated during slow- reflectance and α and S are the absorption and scattering coefficients,
cooling to room temperature. Minor yellow impurities were observed respectively.
forming on the surface of the solution. Yield 415 mg (37.7% based on Steady-State Photoluminescence. Steady-state PL was meas-
total In content). An analogous procedure was used to synthesize ured from samples at 100 K. Crystals were extracted from solution,
BA4AgInBr8 for comparison of the band gap. dried using filter paper, and piled with random orientations on 0.18
Synthesis of PA4AgBiBr8. First, 166.9 mg (1 mmol) of silver acetate mm glass substrates. Substrates were then placed directly on the
and 466 mg (1 mmol) of Bi2O3 were dissolved in 5 mL of HBr. Next, heating/cooling block of a temperature-controlled stage (“cryostage”)
0.5 mL of propylamine was added to the previous solution before (Linkam HFS600E-P). Clear glass windows were used to seal the
heating and stirring at 122 °C for 10 min until the solution turned cryostage. The cryostage was then evacuated to approximately 0.1
clear. Yellow plate-like crystals precipitated during slow-cooling to Torr, placed above the objective of an inverted microscope (Nikon
room temperature. Yield 365 mg (30.5% based on total Bi content). Eclipse Ti-U), and cooled to 100 K by active liquid nitrogen vapor
Analogous procedures were used to synthesize BA4AgBiBr 8, flow using the LNP95 liquid nitrogen cooling system. Crystals were
BDA2AgBiBr8, OCA4AgBiBr8, PA4AgIn0.5Bi0.5Br8 (change to 0.5 illuminated by focusing a 405 nm laser (spot size of approximately 10
mmol Bi2O3 and 0.5 mmol InCl3), and PA4AgSb0.5Bi0.5Br8 (change μm) through a 10× objective with a nominal laser output of
to 0.5 mmol Bi2O3 and 0.5 mmol Sb2O3) for comparison of the band approximately 1 mW (corresponding to approximately 10 W/cm2 at
gaps. the level of the sample). PL was collected by the same 10× objective
Synthesis of PA2CsAgBiBr7 and PA2CsAgIn0.5Bi0.5Br7. First, 166.9 and projected to the entrance slit of an imaging spectrometer
mg (1 mmol) of silver acetate, 212.8 mg (1 mmol) of CsBr, and 466 (Princeton IsoPlane SCT320) with an attached cooled CCD camera
mg (1 mmol) of Bi2O3 were dissolved in 8 mL of HBr. Next, 160 mg (Princeton PIXIS 1024). The excitation wavelengths were filtered out
of propylamine was added to the previous solution before heating and using a conventional three-element 405 nm filter cube (Semrock).

19106 DOI: 10.1021/jacs.9b09945

J. Am. Chem. Soc. 2019, 141, 19099−19109
Journal of the American Chemical Society Article

Integration times were on the order of 10 s. Considering the high

incident optical powers required to get a decent PL signal, we
conclude that PL yields of all materials are remarkably low. No signs
■ ACKNOWLEDGMENTS
This work was supported by the U.S. Department of Energy,
of light-induced material degradation were observed. Office of Science, Basic Energy Sciences, under Grant
Computational Details. Ab initio calculations using VASP were SC0012541. The research reported here made use of the
performed on PA2CsAgBiBr7, PA4AgBiBr8, PA4AgInBr8, PA4AgInCl8, shared facilities of the Materials Research Science and
and BDA2AgBiBr8 using the projector augmented wave method, and Engineering Center at UC Santa Barbara, NSF DMR
results were compared using the PBE and HSE06 functionals with and 1720256. The UCSB MRSEC is a member of the Materials
without SOC.50−54,48,55 For those structures with no partial Research Facilities Network (www.mrfn.org). R.M.K. gratefully
occupancies on the organic spacer molecules, PBE calculations were
acknowledges the National Defense Science and Engineering
performed both on the full, room-temperature, experimental
structures and model “inorganic” structures in which the spacers Graduate fellowship for financial support. This work is
were removed and NH4+ ions replaced with Cs+ ions on the nitrogen supported in part by the project “NANO-TANDEM”
sites. Cesium-substituted inorganic structures are frequently used to (MIS5029191), cofinanced by Greece and the European
simulate the electronic structure of complex hybrid perovskite Regional Development Fund.

■
derivatives and have previously been applied to related compounds.36
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19109 DOI: 10.1021/jacs.9b09945

J. Am. Chem. Soc. 2019, 141, 19099−19109