advances.sciencemag.org/cgi/content/full/3/8/e1701293/DC1

Supplementary Materials for

Enhanced photovoltaic performance and stability with a new

type of hollow 3D perovskite {en}FASnI3

Weijun Ke, Constantinos C. Stoumpos, Menghua Zhu, Lingling Mao, Ioannis Spanopoulos,

Jian Liu, Oleg Y. Kontsevoi, Michelle Chen, Debajit Sarma, Yongbo Zhang,

Michael R. Wasielewski, Mercouri G. Kanatzidis

Published 30 August 2017, Sci. Adv. 3, e1701293 (2017)

DOI: 10.1126/sciadv.1701293

This PDF file includes:

fig. S1. Top-view SEM images of the {en}FASnI3 crystals.

fig. S2. TGA spectra of FAI, enI2, and SnI2 powder.

fig. S3. Top-view SEM images of the {en}FASnI3 perovskite films with various

amounts of en loading.

fig. S4. 1H NMR spectra of the films with and without en loading.

fig. S5. Bandgaps of the {en}FASnI3 perovskite films.

fig. S6. UV-vis optical absorption spectra, J-V, and EQE curves of the perovskite

absorbers with various amounts of en loading.

fig. S7. Air stability of UV-vis absorption spectra and XRD patterns of the

{en}FASnI3 perovskite films.

fig. S8. Thermal stability test of the {en}FASnI3 perovskite films.

fig. S9. Steady-state efficiency of an {en}FASnI3 solar cell with 10% en loading.

fig. S10. J-V curves of {en}FASnI3 solar cells with larger active areas.

table S1. Unit cells, bonding parameters, and refinement parameters of

{en}FASnI3 crystals.

table S2. Comparison of the initial and final FA/en ratio on NMR and density

measurements.

table S3. Comparison of experimental and theoretical crystal densities of all

reported materials.

table S4. Summary of the photovoltaic parameters of the {en}FASnI3 solar cells

with various amounts of en loading.

table S1. Unit cells, bonding parameters, and refinement parameters of {en}FASnI3

crystals.

FASnI3 1:0.1 1:0.25 1:0.5 1:1

a

α

b

β

c

γ

V

6.3097(6) Å

90°

8.9143(8) Å

90°

8.9211(8) Å,

90°

501.78(8) Å3

6.3159(6) Å

90°

8.9340(8) Å

90°

8.9334(8) Å

90°

504.08(11) Å3

6.3446(6) Å

90°

8.9744(8) Å

90°

8.9544(8) Å

90°

509.85(13) Å3

6.3490(11) Å

90°

8.9745(12) Å

90°

8.9746(9) Å

90°

511.36(12) Å3

6.3689(6) Å

90°

9.0070(8) Å

90°

8.9972(8) Å

90°

516.12(13) Å3

Bond lengths [Å]

Label Distance Distance Distance Distance Distance

Sn-I(1)

Sn-I(2)

Sn-I(2)’

3.1556(6)

3.145(3)

3.161(3)

3.1583(7)

3.156(4)

3.161(4)

3.1730(8)

3.161(3)

3.178(4)

3.1746(11)

3.149(4)

3.197(4)

3.1850(8)

3.171(6)

3.196(6)

Bond angles [°]

Label Angle Angle Angle Angle Angle

Sn-I(1)-Sn

Sn-I(2)-Sn 177.74(11)

178.07(8) 178.12(12)

178.29(11) 177.56(12)

178.62(9) 178.94(17)

179.50(12) 177.9(2)

178.22(17)

Label Occupancy Occupancy Occupancy Occupancy Occupancy

Sn 1.011(7)a 0.971(6) 0.936(7) 0.909(7) 0.846(7)

a The occupancy of Sn is 1 within the standard error of the refinement.

table S2. Comparison of the initial and final FA/en ratio on NMR and density

measurements.

Nominal NMR Density

0.1 0.035 0.185

0.25 0.095 0.233

0.5 0.240 0.320

1 0.315 0.500

table S3. Comparison of experimental and theoretical crystal densities of all

reported materials.

Material/Density

(g cm-3) Experiment

FASn1-xenxI3

(Estimated)

FA1-xenx/2SnI3

(Estimated)

FASnI3 3.594(1) 3.604 3.604

1:0.1 3.479(1) 3.550 3.578

1:0.25 3.459(1) 3.455 3.524

1:0.5 3.403(1) 3.353 3.491

1:1 3.285(1) 3.140 3.415

fig. S1. Top-view SEM images of the {en}FASnI3 crystals. Top view SEM images of

the {en}FASnI3 perovskite crystals prepared by the mixed cations of FA and en with

different molar rations of (a) 1:0, (b) 1:0.1, (c) 1:0.25, (d) 1:0.5, and (e) 1:1.

fig. S2. TGA spectra of FAI, enI2, and SnI2 powder.

fig. S3. Top-view SEM images of the {en}FASnI3 perovskite films with various

amounts of en loading. Top view SEM images of the {en}FASnI3 perovskite films

prepared by the FASnI3 precursors with (a) 7.5%, (b) 10%, (c) 12.5, and 15% en loading

grown on mesoporous TiO2.

fig. S4. 1H NMR spectra of the films with and without en loading. 1H NMR spectra

of the films without and with 10% and 100% en loading.

fig. S5. Bandgaps of the {en}FASnI3 perovskite films. Band gaps of the {en}FASnI3

perovskite films with various amounts of en loading.

fig. S6. UV-vis optical absorption spectra, J-V, and EQE curves of the perovskite

absorbers with various amounts of en loading. (a) UV-vis optical absorption spectra of

the {en}FASnI3 perovskite films with various amounts of en loading grown on

mesoporous TiO2. (b) J-V curves of the solar cells using the perovskite absorbers with

various amounts of en loading measured under reverse voltage scan. (c) EQE curves of

the solar cells using the perovskite absorbers with various amounts of en loading.

table S4. Summary of the photovoltaic parameters of the {en}FASnI3 solar cells with

various amounts of en loading.

Voc Jsc FF PCE

[V] [mA cm-2] [%] [%]

7.5% 0.29 23.61 57.35 3.94

10% 0.43 23.22 62.65 6.27

12.5% 0.47 20.04 62.16 5.86

15% 0.51 17.33 61.20 5.43

fig. S7. Air stability of UV-vis absorption spectra and XRD patterns of the

{en}FASnI3 perovskite films. UV-vis absorption spectra and XRD patterns of the

{en}FASnI3 perovskite films (a, c, e) without and (b, d, f) with 10% en loading grown on

mesoporous TiO2, which were exposed to ambient air.

fig. S8. Thermal stability test of the {en}FASnI3 perovskite films. UV-vis absorption

spectra and XRD patterns of the {en}FASnI3 perovskite films (a and c) without and

(b and d) with 10% en loading grown on mesoporous TiO2, which were annealed at

100 °C for 0-40 min in ambient air. (e) Photographs of the films before and after

annealed at 100 °C for 40 min in ambient air.

fig. S9. Steady-state efficiency of an {en}FASnI3 solar cell with 10% en loading.

Steady-state efficiency of a {en}FASnI3 solar cell with 10% en loading at a constant bias

voltage of 0.333 V.

fig. S10. J-V curves of {en}FASnI3 solar cells with larger active areas. J-V curves of

{en}FASnI3 solar cells with active areas of (a) 0.39 cm2 and (b) 1.1 cm2 using perovskite

absorbers with 10% en loading measured under reverse voltage scan.