Supplementary Information for

Structural and thermodynamic limits of layer thickness in 2D halide

perovskites

Chan Myae Myae Soe,a,b,1 GP Nagabhushana, c,d,1 Radha Shivaramaiah, c,d,1 Hsinhan Tsai,e
Wanyi Nie,e Jean-Christophe Blancon,e Ferdinand Melkonyan,a,b Duyen H. Cao,a,b
Boubacar Traoré,f Laurent Pedesseau g Mikaël Kepenekian,f Claudine Katan,f Jacky Even,g
Tobin J. Marks,a,b Alexandra Navrotsky,c.d,2 Aditya D. Mohite,e,3 Constantinos C.
Stoumpos, a,b,3 Mercouri G. Kanatzidis a,b,3
a
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA
b
Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston,
Illinois 60208, USA
c
Peter A. Rock Thermochemistry Laboratory, University of California Davis, Davis, CA 95616
d
Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit,
University of California Davis, Davis, CA 95616
e
Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
f
Univ Rennes, ENSCR, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)
– UMR 6226, F-35000 Rennes, France
g
Univ Rennes, INSA Rennes, CNRS, Institut FOTON – UMR 6082, F-35000 Rennes, France

(M.G.K.) m-kanatzidis@northwestern.edu
(C.C.S.) cstoumpos@materials.uoc.gr
(A.D.M.) aditya.d.mohite@rice.edu

1
www.pnas.org/cgi/doi/10.1073/pnas.1811006115
This PDF file includes:

Supplementary text
Figs. S1 to S10
Tables S1 to S12
References for SI reference citations

Supplementary Information Text

Materials
All reagents were used as received from Sigma Aldrich without further purification: lead
oxide (PbO, 99%), methylamine hydrochloride (MACl, 99%), hydriodic acid (HI, 57 wt%
in H2O), hypophosphorous acid (H3PO2, 50 wt% in H2O), n-butylamine (BA, 99.5%),
poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS, 1.3 wt%
dispersion in H2O, conductive grade), phenyl-C61-butyric acid methyl ester (PC61BM,
99.9%), N,N-dimethylformamide (DMF, anhydrous, 99.8%), dimethylsulfoxide (DMSO,
anhydrous, 99.9%), and chlorobenzene (CB, anhydrous, 99.8%).

Materials Characterization
Single-crystal X-ray diffraction data were collected with an image plate STOE IPDS II
diffractometer using Mo Ka radiation (λ = 0.71073 Å) and operating at 50 kV and 40 mA.
Data reduction and numerical absorption corrections were performed with the X-AREA
suite. Single crystals were mounted on the end of the glass tip directly from the mother
liquor, and the use of glue or dispersion oil was avoided because of the clear deterioration
of the crystals. The structure was solved by charge flipping and refined by full-matrix least
squares on F2 with the Jana2006 package.(1)
High-resolution synchrotron powder diffraction (SXRD) data were collected at beamline
11-BM-B of the Advanced Photon Source (APS), Argonne National Laboratory using λ =
0.517040 Å or λ = 0.459200 Å (for n = 5). Discrete detectors covering an angular range
from 0 to 4º 2θ are scanned over a 25.5o 2 range, with data points collected every 0.001o
2θ and a scan speed of 0.1º/s.
Scanning Electron Microscopy (SEM) images of the perovskite crystals were obtained by
using a Hitachi SU3400 equipped with an electron beam accelerated at 10-20 kV.

2
 A Shimadzu UV-3600 PC double-beam, double-monochromator spectrophotometer was
used to acquire room-temperature optical diffuse reflectance spectra of the powdered
samples in the range of 200-2500 nm. BaSO4 was used as a non-absorbing reflectance
reference, and reflectance data were converted to absorbance data via Kubelka–Munk
transformation.(2)
Photoluminescence spectra were collected on oriented crystals using Horiba LabRam
Evolution high-resolution confocal Raman microscope spectrometer (600 g/mm diffraction
grating) equipped with a diode CW laser (473 nm, 25 mW) and a Synapse CCD camera.
1
H-NMR spectra were recorded on Varian Inova 500 MHz, Agilent DD2 500 MHz, and
Agilent DD MR 400 MHz. NMR samples were prepared by dissolving 30 mg of the
synthesized (BA)2(MA)n-1PbnI3n+1 and MAPbI3 compounds in deuterated DMSO-d6
solvent via mechanical agitation. FTIR spectra were recorded on a Nicolet 6700 IR
spectrometer in the 400−4000 cm−1 spectral region with KBr beam splitter.
Thermogravimetric (TGA) and Differential Scanning Calorimetry (DSC) thermal analyses
were performed in a Netzsch STA 449 F3 Jupiter Simultaneous Thermal Analysis (STA)
instrument. The sample was placed into a 3.4 ml alumina crucible. All samples were
measured under ultra-high purity helium gas (flow of 50 ml/min). Buoyancy effect for
helium was corrected by measuring the empty Al2O3 crucible under the same conditions
used for the samples. Temperature was increased at a rate of 10 K/min. Performance of the
thermo-balance in the STA was verified by using a certified sample of calcium oxalate
monohydrate (European Pharmacopoeia Reference Standard) up to 1000 ºC.

Computational Details
The calculations were performed within DFT(3, 4) as implemented in the SIESTA
package(5) with a basis set of finite-range numerical atomic orbitals. We used generalized
gradient approximation with the Perdew-Burke-Ernzerhof functional(6) to describe the
exchange-correlation term and used norm-conserving Troullier-Martins pseudopotentials
for each atomic species to account for the core electrons.(7) 1s1,2s22p2,2s22p3,5s25p5, and
5d106s26p2 were used as valence electrons for H, C, N, I, and Pb, respectively. The polarized
double-zeta (DZP) basis set with an energy shift of 50 meV and a mesh cutoff of 200
Rydberg was used for the calculations. The Brillouin zone was sampled with 2 x 2 x 6, and

3
2 x 2 x 6 Monkhorst-Pack grids for the primitive cells of the n = 6 and n = 7 (BA)2(MA)n-
1PbnI3n+1 members, respectively. The electronic and dielectric properties were calculated
with the experimental lattice parameters, and atomic coordinates were transformed to their
primitive cells whenever applicable. SOC was taken into account in the calculation of the
electronic band structures, although it was not considered in the high-frequency dielectric
constant computations. For the high-frequency dielectric constant profiles, slabs based on
n = 6 and n = 7 (BA)2(MA)n-1PbnI3n+1 systems were constructed, and an electric field of
0.01 eV/A˚ was applied along the [001] direction with the relaxation of the sole electron
density as described elsewhere.(8, 9)

1H-NMR spectroscopy as a tool for perovskite layer determination

NMR (1H-NMR) spectroscopy is useful in characterizing the hybrid halide
perovskites.(10) This method is particularly true for homologous 2D perovskites, since by
estimating the ratio of the “spacer” and “perovskitizer” cations one can deduce the
perovskite composition indirectly. By dissolving the isolated solids in a polar solvent like
d6-DMSO it is possible to quantify the amounts of BA and MA in the solid by comparing
the ratio of CH3- groups of the two cations (Figure S4). The obtained BA:MA ratios are
characteristic of each n value in the chemical formula, and the results are in remarkably
good agreement with those obtained from SXRD. The n values estimated for the higher n-
members, n = 6 and 7 from NMR analysis are “n ~ 10” and “n ~ 8.5”, respectively, with
the numbers being consistent with the presence of excess MAPbI3 in both materials. n = 6
which appears to have a larger BA:MA ratio than n = 7 also show a larger content of
MAPbI3 which correspond to 50% and 33% excess, respectively, assuming that the
compounds have their idealized 1:2.5 and 1:3 BA:MA ratios. Therefore, 1H NMR can
complement conventional XRD analysis in 2D halide perovskites, which also allows the
determination of the secondary phases including the thermodynamically favorable
MAPbI3.

4
Supplementary Figures

Fig. S1. FTIR spectra of the (BA)2(MA)n-1PbnI3n+1 series (n = 3-7, “9” and )

5
 (A) 100 (B) 100
80 80
% Mass

% Mass
60 60
40 BA MA Pb I 40 BA MA Pb I
2 3 4 13 2 4 5 16
20 n=4 20 n=5
0 0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
(C) 100 (D) 100
80 80
% Mass

60

% Mass
60
40 BA MA Pb I 40 BA MA Pb I
2 5 6 19
2 6 7 22
20 n=6 20 n=7
0 0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
(E) 100 (F) 100
80 80
% Mass

60
% Mass

60
40 40 MAPbI3
"BA2MA8Pb9I28"
20 20 n=
"n = 9"
0 0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
Fig. S2. TGA thermographs of the (BA)2(MA)n-1PbnI3n+1 series. All the compounds exhibit
similar mass loss characteristics corresponding to the initial loss of the organic cations at
~300o, followed by a second mass loss from the decomposition/melting of the inorganic
component at 400-450 oC.

6
Fig. S3. Precession images based on the experimental diffraction images generated from
the single-crystal X-ray diffraction data for (BA)2(MA)5Pb6I19 (n = 6) and BA2MA6Pb7I22
(n = 7). The simulated powder patterns (Cu Kα, λ = 1.5406 Å) represent the idealized
diffraction patterns, whereas the simulated precession patterns ((101) slices, Mo Kα, λ =
0.71073 Å), generated from the raw data, reveal the presence of supercell reflections
characteristic of the ordering along the perovskite stacking direction.

7
Fig. S4. 1H-NMR spectra of the (BA)2(MA)n-1PbnI3n+1 compounds dissolved in deuterated
d6-DMSO. (A) NMR spectrum of MAPbI3 indicating the position of the methyl protons of
CH3NH3+ and the solvent. (B) The NMR spectrum of (BA)2(MA)Pb2I7, highlighting the
clear resolution between the methyl and methylene protons of CH3(CH2)3NH3+ and the
methyl protons of CH3NH3+. The quantification of the methyl groups, presents a reliable
method for determining the BA:MA ratio. (C) Extended NMR spectra of (BA)2(MA)n-
1PbnI3n+1 for n = 3-7 and “n = 9”, illustrating the changes occurring on increasing the
number of layers n. For n > 4 the BA: MA ratios do not match the expected ones. The
mismatch is quantified by estimating the CH3NH3+ excess, under the assumption that all
the remaining material corresponds to MAPbI3. The estimated values are in agreement with
the X-ray diffraction data. Note that the shoulder at δ~7.2 ppm corresponds to the -NH3+
protons and is present in all spectra irrespective of the BA:MA ratio.

8
Fig. S5. Characterization of the “n = 9” compound: (a) PXRD, (b) SEM image, (c) optical
gap, and (d) photoluminescence emission of the crystals. The data suggest that the
compound is very similar to MAPbI3, but the small differences observed in the optical
spectra, as well as the sheet-like morphology of the crystals suggest that the sample likely
contains higher n members of 2D perovskite.

9
Fig. S6. Calculated band structures of the (A) n = 6 and (B) n = 7 members of the
(BA)2(MA)n-1PbnI3n+1 series. (C) Graphical representation of the Γ-point wavefunctions of
the valence (VBM) and conduction (CBM) bands drawn in the primitive unit cell for
(BA)2(MA)6Pb7I22, illustrating the localization of the wavefunction at the band extrema.

10
Fig. S7. AFM images of (BA)2(MA)5Pb6I19 and (BA)2(MA)6Pb7I22 hot-cast films from
mixed DMF/DMSO.

*
Intensity (counts x 10 )

(220)

(A) (B)
(110) n=
Norm. Intensity (a.u.)

* n=5
(111)
*
(202)
"n = 9" 3 n=6
*
n=7 n=7
n=6
2 "n = 9"
n=
n=5
1
n=4
n=3
0
10 20 30 40 50 27 28 29 30
2(deg.) 2(deg.)

Fig. S8. PXRD of the hot-cast films prepared from the (BA)2(MA)n-1PbnI3n+1 series (n = 3-

7, “9”, ). Asterisks indicate the positions of the peaks from the ITO substrate.

11
Fig. S9. Stability test of the hot-cast films prepared from the (BA)2(MA)n-1PbnI3n+1 series

(n = 5-7, “9”, and ) that are subject to ambient air for one month (30-40% RH). Asterisks

indicate the positions of the peaks from PbI2, growing as a second phase over prolonged

exposure of the perovskite in air.

12
 18 18
(A) (B)
Current Density (mA/cm )

Current Density (mA/cm )

n=5 n=6
2

2
15 15
12 12
9 9
6 reverse scan 6 reverse scan
3 forward scan 3 forward scan
0 0
-3 -3
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Voltage (V) Voltage (V)
18 25
(C) (D)
Current Density (mA/cm )

Current Density (mA/cm )

n=7 "n = 9"
2

2
15 20
12
15
9
6 10
reverse scan
3 reverse scan
forward scan 5
forward scan
0
0
-3
-5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8
Voltage (V) Voltage (V)

Fig. S10. Hysteresis trends of the planar solar cell devices from (BA)2(MA)n-1PbnI3n+1
compounds (n = 5-7 and “9”).

13
 Supplementary Tables

Table S1. Crystal data and structure refinement for (C4H9NH3)2(CH3NH3)5Pb6I19 and
(C4H9NH3)2(CH3NH3)6Pb7I22 at 293 K.
Empirical formula (C4H9NH3)2(CH3NH3)5Pb6I19 (C4H9NH3)2(CH3NH3)6Pb7I22
Formula weight 3963 4582.9
Temperature 293 K 293 K
Wavelength 0.71073 Å 0.71073 Å
Crystal system orthorhombic orthorhombic
Space group Cc2m C2cb
a = 8.9051(11) Å a = 8.8998(11) Å
b = 89.424(9) Å, b = 101.959(15) Å,
Unit cell dimensions c = 8.9127(9) Å,
c = 8.8851(10) Å
α = β = γ = 90° α = β = γ = 90°
Volume 7075.4(14) Å3 8087.5(17) Å3
Z 4 4
Density (calculated) 3.7203 g/cm3 3.7639 g/cm3
Absorption coefficient 22.534 mm-1 22.935 mm-1
F(000) 6720 7760
Crystal size 0.2008 x 0.1525 x 0.0308 mm3 0.1322 x 0.0649 x 0.0306 mm3
θ range for data collection 2.3 to 29.31° 3.29 to 24.89°
-12<=h<=12 -9<=h<=10
Index ranges -100<=k<=121 -118<=k<=56
-9<=l<=12 -8<=l<=10
Reflections collected 18326 4567
Independent reflections 5488 [Rint = 0.1482] 2217 [Rint = 0.2887]
Completeness to θ 96% 65%
Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2
Data / restraints /
5488 / 19 / 188 2217 / 10 / 171
parameters
Final R indices [I>2σ(I)] Robs = 0.1376, wRobs = 0.2386 Robs = 0.1913, wRobs = 0.4025
Largest diff. peak and
5.21 and -3.89 e·Å-3 1.58 and -1.47 e·Å-3
hole
R = Σ||Fo|-|Fc|| / Σ|Fo|, wR = {Σ[w(|Fo|2 - |Fc|2)2] / Σ[w(|Fo|4)]}1/2 and w=1/(σ2(I)+0.0004I2)

14
Table S2. Atomic coordinates (x104) and equivalent isotropic displacement parameters
(Å2x103) for (C4H9NH3)2(CH3NH3)5Pb6I19 at 293 K with estimated standard deviations in
parentheses.
Label x y z Occupancy Ueq*
Pb(1) 7489(8) 2281(1) 2500 1 54(3)
Pb(2) 7495(8) 2984(1) 2500 1 53(3)
Pb(3) 7506(8) 1576(1) 2500 1 58(3)
Pb(4) 7507(8) 3690(1) 2500 1 53(3)
Pb(5) 7489(8) 867(1) 2500 1 67(4)
Pb(6) 7496(8) 4400(1) 2500 1 66(4)
I(1) 10000 2240(3) 5000 1 111(9)
I(2) 5000 4369(3) 5000 1 118(9)
I(3) 10000 4441(4) 5000 1 168(16)
I(4) 5000 2301(3) 5000 1 113(11)
I(5) 5000 1534(3) 5000 1 137(11)
I(6) 10000 843(3) 5000 1 129(10)
I(7) 7040(20) 1924(2) 2500 1 109(9)
I(8) 6960(20) 4744(3) 2500 1 176(13)
I(9) 7936(16) 2623(2) 2500 1 117(6)
I(10) 10000 1601(3) 5000 1 121(11)
I(11) 5000 925(3) 5000 1 291(19)
I(12) 5000 2948(3) 5000 1 120(10)
I(13) 10000 3004(2) 5000 1 92(8)
I(14) 5000 3721(3) 5000 1 101(9)
I(15) 7060(20) 3329(2) 2500 1 111(9)
I(16) 10000 3651(3) 5000 1 120(10)
I(17) 7880(20) 4038(2) 2500 1 132(9)
I(18) 6850(20) 540(2) 2500 1 147(10)
I(19) 7983(18) 1225(2) 2500 1 118(9)
N(1) 2050(40) 3966(5) 2500 1 4(11)
C(1) 3020(50) 4103(6) 2500 1 4(11)
N(2) 3070(50) 2634(8) 2500 1 23(15)
C(2) 1970(70) 2507(8) 2500 1 23(15)
N(3) 2150(60) 1954(5) 2500 1 13(14)
C(3) 2910(60) 1805(6) 2500 1 13(14)
N(4) 2110(70) 3359(7) 2500 1 32(18)

15
C(4) 3000(80) 3216(8) 2500 1 32(18)
N(5) 2450(60) 1210(12) 2500 1 260(80)
C(5) 1400(170) 1080(20) 2500 1 260(80)
N(6) 4720(30) 4601(2) 2500 1 600(200)
C(6) 4190(110) 4760(2) 2500 1 600(200)
C(7) 2500(120) 4763(10) 2500 1 600(200)
C(8) 2000(200) 4922(13) 2500 1 600(200)
C(9) 300(200) 4930(20) 2500 1 600(200)
N(7) 3353(19) 727(2) 2500 1 700(200)
C(10) 3260(110) 559(2) 2500 1 700(200)
C(11) 1640(140) 513(7) 2500 1 700(200)
C(12) 1500(200) 345(7) 2500 1 700(200)
C(13) -100(300) 298(16) 2500 1 700(200)
H(1c1) 3011.52 4147.24 1515.98 0.5 4.3
H(2c1) 2638.16 4173.32 3220.13 0.5 4.3
H(3c1) 4030.36 4076.07 2763.9 0.5 4.3
H(1c2) 1850.64 2469.61 1494.15 0.5 27.3
H(2c2) 2324.25 2428.54 3142.42 0.5 27.3
H(3c2) 1013.45 2542.23 2863.43 0.5 27.3
H(1c3) 3198.51 1779.03 1491.45 0.5 15.5
H(2c3) 3785.64 1808.43 3128.29 0.5 15.5
H(3c3) 2228.44 1730.46 2880.27 0.5 15.5
H(1c4) 2764.48 3159.32 1617.59 0.5 38
H(2c4) 4056.8 3239.8 2500 1 38
H(3c4) 2763.86 3159.28 3381.98 0.5 38
H(1c5) 1883.22 994.89 2052.24 0.5 317.5
H(2c5) 1117.88 1056.24 3516.28 0.5 317.5
H(3c5) 515.09 1104.56 1931.49 0.5 317.5
H(1c6) 4554.4 4809.91 3382.22 0.5 737.8
H(2c6) 4554.4 4809.91 1617.78 0.5 737.8
H(1c7) 2131.81 4713.41 1617.81 0.5 737.8
H(2c7) 2131.81 4713.41 3382.19 0.5 737.8
H(1c8) 2340.07 4972.42 1617.8 0.5 737.8
H(2c8) 2340.07 4972.42 3382.2 0.5 737.8
H(1c9) -52.73 5027.7 2500 1 737.8
H(2c9) -82.6 4875.91 1617.81 0.5 737.8

16
H(3c9) -82.6 4875.91 3382.19 0.5 737.8
H(1c10) 3744.16 520.79 1617.8 0.5 794.5
H(2c10) 3744.16 520.79 3382.2 0.5 794.5
H(1c11) 1152.92 551.22 3382.21 0.5 794.5
H(2c11) 1152.92 551.22 1617.79 0.5 794.5
H(1c12) 2030.53 306.53 1617.79 0.5 794.5
H(2c12) 2030.53 306.53 3382.21 0.5 794.5
H(1c13) -135.45 191.17 2500 1 794.5
H(2c13) -560.75 336.96 3382.19 0.5 794.5
H(3c13) -560.75 336.96 1617.81 0.5 794.5
H(1n1) 1786.95 3944.55 1581.92 0.5 4.3
H(2n1) 2554.94 3890.91 2875.26 0.5 4.3
H(3n1) 1256.03 3981.64 3042.83 0.5 4.3
H(1n4) 1269.86 3344.53 2023.52 0.5 38
H(2n4) 1924.13 3385.28 3423.01 0.5 38
H(3n4) 2622.29 3428.75 2053.48 0.5 38
H(1n5) 1966.47 1291.11 2252.64 0.5 317.5
H(2n5) 2836.89 1221.34 3393.93 0.5 317.5
H(3n5) 3169.89 1194.65 1853.42 0.5 317.5
H(1n6) 5692.07 4598.89 2500 1 737.8
H(2n6) 4380.63 4555.58 3299.49 0.5 737.8
H(3n6) 4380.63 4555.58 1700.51 0.5 737.8
H(1n7) 4291.59 754.01 2500 1 794.5
H(2n7) 2912.2 761.86 1700.51 0.5 794.5
H(3n7) 2912.2 761.86 3299.49 0.5 794.5
H(1n2) 3601.39 2630.66 1677.75 0.5 27.3
H(2n2) 2591.96 2718.21 2547.66 0.5 27.3
H(3n2) 3663.49 2625.28 3274.59 0.5 27.3
H(1n3) 1203.19 1943.23 2700.18 0.5 15.5
H(2n3) 2562.76 2011.3 3180.37 0.5 15.5
H(3n3) 2253.68 1995.82 1619.45 0.5 15.5

17
Table S3. Anisotropic displacement parameters (Å2x103) for (C4H9NH3)2(CH3NH3)5Pb6I19
at 293 K with estimated standard deviations in parentheses.
Label U11 U22 U33 U12 U13 U23
Pb(1) 65(6) 54(4) 44(6) -8(4) 0 0
Pb(2) 68(6) 45(4) 46(7) 0(4) 0 0
Pb(3) 64(6) 54(4) 57(7) -7(4) 0 0
Pb(4) 62(6) 54(4) 44(6) 1(4) 0 0
Pb(5) 92(8) 58(5) 50(7) 13(5) 0 0
Pb(6) 74(7) 87(6) 37(6) 17(5) 0 0
I(1) 118(16) 131(17) 83(13) 0 -70(9) 0
I(2) 120(15) 180(20) 55(11) 0 -6(7) 0
I(3) 86(16) 300(40) 110(20) 0 -13(9) 0
I(4) 100(16) 170(30) 63(14) 0 25(8) 0
I(5) 136(18) 200(30) 77(13) 0 81(10) 0
I(6) 149(16) 200(20) 38(7) 0 -70(9) 0
I(7) 102(11) 45(7) 180(20) -44(8) 0 0
I(8) 100(12) 143(18) 280(30) -79(12) 0 0
I(9) 135(10) 35(7) 180(15) 47(11) 0 0
I(10) 115(17) 170(20) 78(15) 0 -35(10) 0
I(11) 173(17) 150(20) 550(50) 0 270(20) 0
I(12) 140(20) 134(18) 82(15) 0 75(10) 0
I(13) 80(13) 116(15) 79(14) 0 -16(7) 0
I(14) 72(12) 180(20) 53(11) 0 7(6) 0
I(15) 103(12) 42(7) 190(20) -46(8) 0 0
I(16) 134(19) 140(20) 89(15) 0 -76(11) 0
I(17) 139(14) 64(10) 190(20) 73(10) 0 0
I(18) 127(14) 44(7) 270(30) -62(8) 0 0
I(19) 74(9) 75(10) 210(20) 42(9) 0 0

18
Table S4. Bond lengths [Å] for (C4H9NH3)2(CH3NH3)5Pb6I19 at 293 K with estimated
standard deviations in parentheses.
Label Distances
Pb(1)-I(1) 3.170(5)
Pb(1)-I(4) 3.147(5)
Pb(1)-I(7) 3.199(17)
Pb(1)-I(9) 3.103(19)
Pb(2)-I(9) 3.229(19)
Pb(2)-I(12) 3.158(6)
Pb(2)-I(13) 3.152(5)
Pb(2)-I(15) 3.116(16)
Pb(3)-I(5) 3.167(6)
Pb(3)-I(7) 3.156(17)
Pb(3)-I(10) 3.149(6)
Pb(3)-I(19) 3.126(19)
Pb(4)-I(14) 3.160(5)
Pb(4)-I(15) 3.250(16)
Pb(4)-I(16) 3.158(5)
Pb(4)-I(17) 3.134(19)
Pb(5)-I(6) 3.160(6)
Pb(5)-I(11) 3.184(7)
Pb(5)-I(18) 2.997(17)
Pb(5)-I(19) 3.273(18)
Pb(6)-I(2) 3.151(5)
Pb(6)-I(3) 3.171(6)
Pb(6)-I(8) 3.10(2)
Pb(6)-I(17) 3.246(19)

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Table S5. Bond angles [°] for (C4H9NH3)2(CH3NH3)5Pb6I19 at 293 K with estimated
standard deviations in parentheses.
Label Angles
Pb(1)-I(1)-Pb(1)’ 166.7(8)
Pb(6)-I(2)-Pb(6)’ 169.4(9)
Pb(6)-I(3)-Pb(6)’ 167.2(12)
Pb(1)-I(4)-Pb(1)’ 173.3(9)
Pb(1)-I(7)-Pb(3) 165.5(6)
Pb(1)-I(9)-Pb(2) 165.4(5)
Pb(3)-I(10)-Pb(3)’ 172.5(9)
Pb(5)-I(11)-Pb(5)’ 161.4(9)
Pb(2)-I(12)-Pb(2)’ 168.2(8)
Pb(2)-I(13)-Pb(2)’ 173.2(8)
Pb(4)-I(14)-Pb(4)’ 170.1(9)
Pb(2)-I(15)-Pb(4) 165.5(7)
Pb(4)-I(16)-Pb(4)’ 167.1(9)
Pb(4)-I(17)-Pb(6) 167.6(7)
Pb(3)-I(19)-Pb(5) 164.8(6)

Table S6. Atomic coordinates (x104) and equivalent isotropic displacement parameters
(Å2x103) for (C4H9NH3)2(CH3NH3)6Pb7I22 at 293 K with estimated standard deviations in
parentheses.
Label x y z Occupancy Ueq*
Pb(1) 5314(18) 0 5000 1 90(5)
Pb(2) 5217(14) 618(1) 5000(4) 1 77(3)
Pb(3) 5144(12) 1237(1) 5001(4) 1 79(3)
Pb(4) 5163(12) 1859(2) 5004(5) 1 129(5)
I(1) 7040(30) -18(4) 2270(20) 1 310(20)
I(2) 2490(40) 1259(6) 7390(20) 1 230(30)
I(3) 2520(30) 652(6) 2670(30) 1 300(30)
I(4) 160(20) 1540(2) 433(16) 1 167(10)
I(5) 50(20) 921(2) 9585(19) 1 196(12)
I(6) 2650(40) 1874(9) 2516(18) 1 310(50)
I(7) 7400(30) 570(5) 7700(20) 1 195(17)
I(8) 7590(40) 1797(9) 7562(17) 1 240(30)
I(9) 5180(30) 310(2) 4614(19) 1 170(9)

20
I(10) 7420(30) 1203(5) 2362(19) 1 166(16)
I(11) 5220(30) 2147(3) 5504(17) 1 248(15)
N(1) 540(60) 314(8) 5530(60) 1 25(13)
N(2) 670(60) 1621(9) 6880(60) 1 52(19)
N(3) 340(80) 802(7) 2610(40) 1 28(14)
N(4) 320(80) 2057(5) 5160(50) 1 37(11)
C(1) 740(60) 383(8) 7000(70) 1 25(13)
C(2) 480(90) 1634(11) 5220(60) 1 52(19)
C(3) 330(90) 905(6) 3800(70) 1 28(14)
C(4) 530(70) 2203(6) 5090(50) 1 37(11)
C(5) 650(40) 2245(6) 3480(60) 1 37(11)
C(6) 2270(40) 2253(7) 3030(70) 1 37(11)
C(7) 2630(70) 2389(8) 2530(110) 1 37(11)
H(1n1) 942.96 360.83 4816.35 1 29.9
H(2n1) 984.28 237.82 5564.02 1 29.9
H(3n1) -409.29 303.07 5346.42 1 29.9
H(1n2) -84.67 1656.7 7341.09 1 61.9
H(2n2) 720.94 1537.92 7123.19 1 61.9
H(3n2) 1500.48 1659.49 7155.5 1 61.9
H(1n3) 243.8 724.67 3015.57 1 33.4
H(2n3) -394.3 815.16 1984.42 1 33.4
H(3n3) 1191.88 805.03 2121.37 1 33.4
H(1n4) 1184.12 2019.96 5324.11 1 44
H(2n4) -293.33 2038.34 5889.95 1 44
H(3n4) -49.37 2029.36 4318.01 1 44
H(1c1) -99.36 440.63 7166.66 1 29.9
H(2c1) 780.88 319.29 7794.65 1 29.9
H(3c1) 1650.52 432.8 6986.25 1 29.9
H(1c2) 684.78 1722.29 4923.38 1 61.9
H(2c2) 1154.21 1575.21 4716.34 1 61.9
H(3c2) -539.8 1611.81 4955.37 1 61.9
H(1c3) 350.39 863.88 4771.77 1 33.4
H(2c3) 1189.94 960.58 3691.41 1 33.4
H(3c3) -570.81 956.57 3711.84 1 33.4
H(1c4) 1431.78 2227.17 5608.66 1 44
H(2c4) -315.32 2245.96 5543.96 1 44

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 H(1c5) 143.02 2182.22 2850.96 1 44
H(2c5) 189.63 2329.51 3353.79 1 44
H(1c6) 2462.28 2192.43 2227.87 1 44
H(2c6) 2889.41 2229.96 3879.42 1 44
H(1c7) 2144.67 2451.17 3183.49 1 44
H(2c7) 3701.66 2402.75 2575.37 1 44
H(3c7) 2289.71 2401.87 1523.77 1 44

Table S7. Anisotropic displacement parameters (Å2x103) for (C4H9NH3)2(CH3NH3)6Pb7I22

at 293 K with estimated standard deviations in parentheses.
Label U11 U22 U33 U12 U13 U23
Pb(1) 40(6) 162(13) 67(5) 0 0 -3(5)
Pb(2) 51(4) 109(7) 70(4) 15(5) 2(2) -3(3)
Pb(3) 51(4) 125(7) 61(3) -12(5) 0(2) -4(3)
Pb(4) 61(5) 283(15) 43(3) -13(11) 4(3) -10(4)
I(1) 200(20) 550(70) 180(20) -290(30) -91(15) 180(30)
I(2) 96(19) 460(70) 149(19) 80(30) 46(9) -120(20)
I(3) 72(16) 600(90) 210(30) 70(30) -61(12) 160(30)
I(4) 208(15) 150(20) 143(12) 32(17) 93(13) -8(12)
I(5) 210(18) 190(30) 182(14) 90(19) -112(14) -3(14)
I(6) 81(17) 800(130) 60(13) -20(30) -32(5) 90(20)
I(7) 64(13) 350(50) 170(19) -23(16) -26(9) -20(20)
I(8) 89(17) 590(70) 49(11) -10(30) -35(6) -26(18)
I(9) 243(19) 83(16) 182(13) 34(17) -112(15) -17(12)
I(10) 63(15) 300(40) 129(15) -22(16) 26(7) 49(16)
I(11) 264(18) 380(40) 103(11) 30(30) 79(15) 20(18)

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Table S8. Bond lengths [Å] for (C4H9NH3)2(CH3NH3)6Pb7I22 at 293 K with estimated
standard deviations in parentheses.
Label Distances
Pb(1)-I(1) 2.88(3)
Pb(1)-I(1)’ 3.55(3)
Pb(1)-I(9) 3.19(2)
Pb(2)-I(3) 3.19(3)
Pb(2)-I(5) 3.12(2)
Pb(2)-I(7) 3.13(3)
Pb(2)-I(7)’ 3.28(3)
Pb(2)-I(9) 3.15(2)
Pb(3)-I(2) 3.19(3)
Pb(3)-I(2)’ 3.14(3)
Pb(3)-I(4) 3.11(2)
Pb(3)-I(5) 3.24(2)
Pb(3)-I(10) 3.12(2)
Pb(3)-I(10)’ 3.23(3)
Pb(4)-I(4)’ 3.27(2)
Pb(4)-I(6) 3.15(3)
Pb(4)-I(6)’ 3.16(3)
Pb(4)-I(8) 3.20(3)
Pb(4)-I(8)’ 3.22(3)
Pb(4)-I(11) 2.97(3)

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Table S9. Bond angles [°] for (C4H9NH3)2(CH3NH3)6Pb7I22 at 293 K with estimated
standard deviations in parentheses.
Label Angles
Pb(1)-I(1)-Pb(1)’ 156.0(10)
Pb(2)-I(3)-Pb(2)’ 164.7(18)
Pb(3) -I(4)-Pb(4) 166.0(5)
Pb(2) -I(5)-Pb(3) 166.0(6)
Pb(4)-I(6)-Pb(4)’ 174.0(3)
Pb(2)-I(7)-Pb(2)’ 158.8(16)
Pb(4)-I(8)-Pb(4)’ 157.0(3)
Pb(1)-I(9)-Pb(2) 167.2(6)
Pb(3)-I(10)-Pb(3)’ 164.9(17)

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Table S10. Thermochemical data used for the calculation of enthalpy of formation of 2D

halide (BA)2(MA)n-1PbnI3n+1 perovskite.

Compound n ΔHs (kJ/mol) Enthalpy of formation (kJ/mol)

BA - 3.34±0.299 (4)

PbI2 - 33.28±0.55(4)

MAI - 19.60 ± 0.11(4)

BA2PbI4 1 89.65±1.01(4) -49.69±1.18

BA2MAPb2I7 2 160.74±1.36(4) -67.90±1.47

BA2MA2Pb3I10 3 174.46±1.12(4) -28.74±1.25

BA2MA3Pb4I13 4 279.22±3.06(5) -80.62±3.12

BA2MA4Pb5I16 5 271.95±2.02(5) -20.47±2.11

BA2MA5Pb6I19 6 164.77±1.34(4) 138.59±1.48

BA2MA6Pb7I22 7 115.18±1.87(4) 242.06±1.97

MAPbI3(11) ∞ 18.38 ± 0.85(4) 34.50  1.01

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Table S11. Best-performing photovoltaic parameters of the planar solar cell devices from
(BA)2(MA)n-1PbnI3n+1 compounds (n =3-7 and “9”) shown in Figure 6a.

n Jsc [mA/cm2] Voc [V] FF [%] Eta [%]

3 14.37 1.06 75.39 11.44(12)
4 16.76 1.01 74.13 12.52(12)
5 15.50 0.986 65.51 10.00(13)
6 16.30 1.05 63.50 10.90
7 16.73 0.950 56.03 8.93
“9” 21.84 0.801 72.19 12.63

Table S12. The synthetic protocol used for the synthesis of (CH3(CH2)3NH3)n(CH3NH3)n-
1PbnI3n+1 homologous perovskites using the off stoichiometry approach.

Precursor amount (1 mmol basis)

(CH3(CH2)3NH2 (CH3NH3)Cl PbO
99.2μL 67.52 mg 223.2 mg

Targeted composition n n-1 Reaction amounts on a 20 mmol scale

(CH3(CH2)3NH3)2PbI4 1 0 1984.00 0.00 4464
(CH3(CH2)3NH3)2(CH3NH3)Pb2I7 2 1 992.00 675.20 4464
(CH3(CH2)3NH3)2(CH3NH3)2Pb3I10 3 2 661.33 900.27 4464
(CH3(CH2)3NH3)2(CH3NH3)3Pb4I13 4 3 496.00 1012.80 4464
(CH3(CH2)3NH3)2(CH3NH3)4Pb5I16 5 4 396.80 1080.32 4464
(CH3(CH2)3NH3)2(CH3NH3)5Pb6I19 6 5 330.67 1125.33 4464
(CH3(CH2)3NH3)2(CH3NH3)6Pb7I22 7 6 283.43 1157.46 4464
(CH3(CH2)3NH3)2(CH3NH3)7Pb8I25 8 7 248.00 1181.60 4464
(CH3(CH2)3NH3)2(CH3NH3)8Pb9I28 9 8 220.44 1200.36 4464
(CH3(CH2)3NH3)2(CH3NH3)9Pb10I31 10 9 198.40 1215.36 4464
(CH3NH3)PbI3 ∞ ∞ 0.00 1350.04 4464

26
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