Supplementary Materials for - Science...2020/10/02 · non-reflective metal mask with an aperture...
Transcript of Supplementary Materials for - Science...2020/10/02 · non-reflective metal mask with an aperture...
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science.sciencemag.org/content/370/6512/eabb8985/suppl/DC1
Supplementary Materials for
Vapor-assisted deposition of highly efficient, stable black-phase
FAPbI3 perovskite solar cells
Haizhou Lu, Yuhang Liu, Paramvir Ahlawat, Aditya Mishra, Wolfgang R. Tress, Felix T.
Eickemeyer, Yingguo Yang, Fan Fu, Zaiwei Wang, Claudia E. Avalos, Brian I. Carlsen, Anand
Agarwalla, Xin Zhang, Xiaoguo Li, Yiqiang Zhan*, Shaik M. Zakeeruddin, Lyndon Emsley,
Ursula Rothlisberger, Lirong Zheng*, Anders Hagfeldt*, Michael Grätzel*
*Corresponding author. Email: [email protected] (Y.Z.); [email protected] L.Z.); [email protected]
(A.H.); [email protected] (M.G.)
Published 2 October 2020, Science 370, eabb8985 (2020)
DOI: 10.1126/science.abb8985
This PDF file includes:
Materials and Methods
Supplementary Text
Figs. S1 to S27
Captions for Movies S1 to S7
References
Other Supplementary Material for this manuscript includes the following:
(available at science.sciencemag.org/content/370/6512/eabb8985/suppl/DC1)
Movies S1 to S7
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Materials and Methods
Materials
Formamidinium iodide (FAI) and formamidinium thiocyanate (FASCN) were purchased
from Great Solar Australia Pty Ltd. Lead iodide (PbI2) and tin oxide (SnO2) colloid precursor were
purchased from Alfa Aesar. Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI) and 4-tert-
butyl-pyridine (tbp) were purchased from Sigma-Aldrich. Spiro-OMeTAD was purchased from
Xi’an Polymer Light Technology Corp. Methylamine thiocyanate (MASCN) was purchased from
Tokyo Chemical Industry Co., LTD. N, N-dimethylformamide (DMF), N-Methyl-2-Pyrrolidone
(NMP), chlorobenzene (CB), isopropanol (IPA), and acetonitrile (ACN) were purchased from
Acros Organics. All materials were used as received without further modifications.
Solar cell fabrication
SnO2 layer was spin-coated onto the cleaned ITO substrates from a diluted SnO2 nanoparticle
solution (2.67 wt%) at a spin speed of 4000 rpm for 30 s with additional post annealing at 150 ℃
for 30 mins (5). As fabricated SnO2 layer was treated with UV-ozone for 15 mins just before the
FAPbI3 perovskite layer deposition. The perovskite precursor solution was prepared by mixing
172 mg FAI and 461 mg PbI2 with 600 µL DMF and 100 µL NMP. The perovskite layer was
fabricated by spin coating 30 µL perovskite precursor solution on top of the SnO2 layer at a speed
of 5000 rpm for 30 s inside a dry air glovebox (relative humidity < 5%). At the time of 15 s to the
end, 200 µL CB was quickly dropped as an antisolvent. For the reference FAPbI3 perovskite, the
as fabricated film was annealed at 100 ℃ for 1 min and then at 150 ℃ for 20 mins. For the vapor-
treated perovskite, the as fabricated FAPbI3 perovskite film was firstly annealed at 100 ℃ for 1
min. Then, the perovskite film was put into MASCN/FASCN environment for 5 s until it turns to
black. Finally, the perovskite film was further annealed at 150 ℃ for 20 mins. MASCN/FASCN
solution (3 mg/mL in IPA) was dipped onto a metal sheet and annealed at 100 ℃ for 1 min to
generate the vapor environment. After cooling down the perovskite film on the bench, choline
chloride solution (1mg/mL in IPA) was used to passivate the surface. Then, doped Spiro-OMeTAD
solution (72.3 mg/mL in chlorobenzene) was spin-coated on top of the perovskite layer at a speed
of 3000 rpm for 30 s. For 1 mL Spiro-OMeTAD solution, 17.5 µL Li-TFSI (520 mg/mL in
acetonitrile), 29 µL tbp and 2.5 mg ADAHI (detailed synthesis can be found in reference (39))
were added as dopants. Finally, an 80-nm gold layer was evaporated under high vacuum at a rate
of 0.01 nm/s.
Photovoltaic device testing
Photocurrent density-voltage (J-V) curves were measured using a Keithley 2400 source meter
together with a Xenon arc lamp based solar simulator. The solar simulator was calibrated to AM
1.5G illumination (100 mW/cm2) using a calibrated reference silicon solar cell. All J-V
measurements were performed under a constant scan speed of 10 mV/s inside a box purged with
cool dry air. The photovoltaic data were collected without any device preconditioning. A black,
non-reflective metal mask with an aperture area of 0.16 cm2 was used to cover the active area (~
0.27 cm2) of the device to avoid the artefacts produced by scattered light.
Incident photon-to-electron conversion efficiency (IPCE) measurement
IPCE was measured with a commercial apparatus (Arkeo-Ariadne, Cicci Research s.r.l) based
on a 300 W Xenon lamp. It was recorded as a function of wavelength under a constant white light
bias of approximately 5 mW/cm2 supplied by an array of white light emitting diodes. For all
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measurements, a non-reflective metal mask with an aperture area of 0.16 cm2 was used to cover
the active area of the device to avoid light scattering through the sides.
External quantum efficiency of the electroluminescence (EQEEL) measurement
To measure the EQEEL, the emitted photon flux was recorded using a calibrated, large area
(1cm2) Si photodiode (Hamamatsu S1227-1010BQ) by applying different bias voltage or current
to the FAPbI3 PSC device with a Bio-logic SP300 potentiostat. All measurements were performed
in the ambient environment (relative humidity is ~30% and environmental temperature is ~23 ℃).
Stability measurement
Stability measurements were performed with a Biologic MPG2 potentiostat under a LED lamp
which was adjusted to the AM 1.5G illumination (100 mW/cm2). The devices (unencapsulated)
were masked (0.16 cm2) and put inside a homemade sample holder purged with nitrogen during
the whole measurements. The devices were measured with a maximum power point (MPP)
tracking routine under continuous one sun illumination. The MPP measurement was updated every
60 s by a standard perturb and observe method. The temperature of the device was controlled at
25 ℃ by a Peltier element in direct contact with the devices. The temperature was measured with
a surface thermometer located between the Peltier element and the device. Both reverse and
forward scanned J-V curves were recorded every 30 mins.
Characterization
Scanning electron microscopy (SEM) images were taken using a high-resolution scanning
microscope (ZEISS Merlin). The X-ray diffraction patterns were performed using Cu Kα radiation
as the X-ray source. Ultraviolet-visible (UV-vis) spectra were measured with a Varian Cary 5.
Photoluminescence (PL) spectra were recorded using Fluorolog 322 (Horiba Jobin Ybon Ltd) with
an excitation wavelength at 460 nm. Time-resolved PL (TRPL) measurement was performed
using Fluorolog 322 spectrofluorometer (Horiba Jobin Yvon, Ltd). A NanoLED-637L (Horiba)
laser diode (637 nm) was used for excitation. The samples were mounted at 60° and the emission
collected at 90° from the incident beam path. The detection monochromator was set to 650 nm and
the PL was recorded using a picosecond photodetection module (TBX-04, Horiba Scientific).
Surface roughness measurements were taken with a Cypher S atomic force microscope (AFM)
from Asylum Research under ambient conditions. An Olympus AC240-TS tip was employed, and
the system was operated under tapping mode.
Solid-state NMR measurement
Room-temperature 1H (900 MHz) and 14N (65.04 MHz) NMR spectra were recorded on a
Bruker Avance Neo 21.1 T spectrometer equipped with a 3.2 mm low-temperature CPMAS probe. 133Cs shifts were referenced to 1 M aqueous solution of CsCl, using solid CsI (δ=271.05 ppm) as
a secondary reference. 1H chemical shifts were referenced to solid adamantane (δH=1.91 ppm). 14N
chemical shifts were referenced to solid adamantane (δH= 0 ppm). Quantitative echo-detected 1H
spectra used a recycle delay of 2 to 50 s. Peak widths were fitted in Topspin 3.2 and the
uncertainties were given at one standard deviation.
Computational method
We constructed a large super-cell of δ-phase FAPbI3 with 28800 atoms (2400 stoichiometric
units of FAPbI3). To perform molecular dynamics (MD) simulations of FAPbI3, we followed a
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similar procedure as used in our previous work (50). Polytypes play an important role in
crystallization of FAPbI3. Therefore, we also upgraded the previously used force field to be able
to simulate all the experimentally known polytypes (2H, 4H, 6H and 3C) of FAPbI3. At first, we
equilibrated this super-cell by performing 10 ns variable-cell isothermal-isobaric simulations at
370 K. Next, we exposed this super-cell to MA+ and SCN- ions (fig. S6). With this set-up, we
again performed an equilibrium run for 2 ns in isothermal-isobaric ensemble at 370 K with a force
field for SCN- ions available from literature (51). Interaction parameters between different
heterogeneous species were calculated with mixing rules. All production runs were performed in
isothermal-isobaric ensemble ranging from 20-100 ns. All simulations were performed with the
Large-Scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) code (31 Mar 2017)
(52). We used a 1.0 nm cutoff for nonbonded interactions, SHAKE (53) for constraints and
particle-particle-particle-mesh Ewald for electrostatic interactions. We used a velocity rescaling
thermostat (54) with a relaxation time of 0.1 ps and a Parrinello-Rahman barostat (55) to keep the
pressure at atmospheric pressure with a relaxation time of 10 ps.
DFT calculations of 4H and 2H polytype with SCN-
First, we replaced up to 50% I- with SCN- ions in the 2H (δ-phase) and 4H-FAPbI3 crystal
structures (56). Then, we performed variable cell first-principles density functional theory (DFT)
calculations of these structures with Generalized Gradient Approximation (GGA) in the Perdew-
Burke-Ernzerhof formulation revised for solids (PBEsol) (57). We used Quantum Espresso (58)
with ultra-soft pseudo-potentials for valence-core electron interactions with a plane wave basis set
of 60 Ry kinetic energy cutoff and 420 Ry density cutoff. The Brillouin zone was sampled by a
2x2x2 k-points grid for 192 atoms supercell of 4H-FAPbI3 and equivalent of 2H structures. The
optimized structures are shown in the supplementary materials.
Details of the DFT calculations for the energy barrier
We first identified a possible phase transition pathway between δ and α-phases of FAPbI3. In
order to generate initial transition structures, we explored the phase space between δ and α-phases
of FAPbI3 with classical MD simulations at different temperatures and interpolated the coordinates
(Pb2+ and I-) along a path from face-sharing to edge-sharing to corner-sharing structures. We would
like to note that here we depicted only one possible transformation pathway (fig. S13), bur that the
system can also go through many different phase transition pathways. To calculate the potential
energy, landscape of this transition pathway we performed variable-cell enthalpic optimization for
each structure with first-principles DFT calculations. For DFT calculations, we used Quantum
Espresso (58) with ultra-soft pseudo-potentials for valence-core electron interactions with a plane
wave basis set of 60 Ry kinetic energy cut-off and 420 Ry density cut-off. All DFT calculations
for the energy barrier used Generalized Gradient Approximation (GGA) and Perdew-Burke-
Ernzerhof (PBE) (59) functional with D3-vdW (60) dispersion corrections. The Brillouin zone was
sampled by a 3×3×3 k-points grid for 96 atoms (2×2×2 supercell) supercell of α-FAPbI3 and
equivalent for other structures. The eanergetic profile along the hypothetical pathway (fig. S13)
provided a first rough estimate of the possible height of the energy barrier involved in the transition
between the two phses, however, the real physical transition might occur along a different path
and the calculations along the sequence of structures (fig. S13) did not include the transition states
involved in going from one intermediate to the next one that might involve even higher energy
points.
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Ab-initio MD of SCN- vapor on δ-phase
An initial configuration, as depicted in fig. S8 was created by putting 14 SCN- ions in a box
with a 192 atoms supercell of δ-phase FAPbI3. Constant temperature and constant volume (NVT)
Born-Oppenheimer MD (BOMD) simulations were performed with the CP2K package (61, 62).
We used a time step of 1fs and a Nose-Hoover chain (63) for temperature control. We performed
BOMD simulations at two different temperatures: 300 and 400 K. All simulations used DFT at the
PBE+D3 (59, 60) level with double-zeta basis sets (DZVP-MOLOPT for Pb, I, S, C, N, H) (64)
and Goedecker-Teter-Hutter (GTH) pseudopotentials (65) with 560 Ry density cut-off.
Ab-initio MD of homogeneous mixture of ions
We performed constant temperature and constant pressure (NPT) simulations of a
homogeneous mixture of ions: 4 Pb2+, 9 I-, 9 SCN-, 5FA+ and 5MA+ as depicted in fig. S9. We
used a similar quantum-mechanical set-up for the BOMD as described in the section above. A
Nose-Hoover chain (63) was used for controlling temperature and the barostat by Martyna et al.
(66) was used for pressure control. We performed simulations at two different temperatures: 350
and 400 K at a pressure of 1atm.
Two-dimensional grazing-incidence XRD (2D-GIXRD) measurement
The 2D-GIXRD measurements were performed at the BL14B1 beamline of the Shanghai
Synchrotron Radiation Facility (SSRF) using X-ray with a wavelength of 0.6887 Å. 2D-GIXRD
patterns were acquired by a MarCCD mounted vertically at a distance of ~632 mm from the sample
with grazing incidence angles of 0.05°, 0.10° and 0.40°, and the exposure time of 30 s.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurement
ToF-SIMS measurements were performed on a ToF-SIMS.5 instrument from IONTOF, Germany,
operated in spectral mode using a 25 keV Bi3+ primary ion beam with an ion current of 0.57 pA.
A mass resolving power in the range of 7000-10000 m/Δm was reached. For depth profiling, a 500
eV Cs+ sputter beam with a current of 25.36 nA was used to remove the material layer-by-layer in
interlaced mode from a raster area of 300 μm × 300 μm. Both positive and negative ions were
collected for depth profile analysis. The mass-spectrometry was performed on an area of 100 μm
× 100 μm in the center of the sputter crater.
Supplementary Text
Note 1. Calculations of MA amount
x = MA integral / # MA[1H]
y = FA integral / # FA[1H]
MA amount = x/y * FA amount
x = 2.0817/6 = 0.34695, y = 97.9183/5 = 19.58366
MA amount = 0.01771630022 * FA amount
MA amount = 1.77 % of FA amount
Note 2. Determination of the Urbach energy 𝐸𝑢, the radiative limit 𝑉oc,rad, the measured Voc and the effect of temperature.
For the determination of 𝑉oc,rad and 𝐸𝑢 , we follow the work of Tress et al. (41). From the electroluminescence 𝐽em(V) (Fig. 4E) at voltage V = 1.0 V, we calculated the spectral shape of
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the absorptance 𝑎(𝐸)~𝐽𝑒𝑚(𝑉)
𝛷𝐵𝐵(𝐸), where 𝛷𝐵𝐵(𝐸) =
1
4𝜋2ℏ3𝑐2𝐸2
exp (𝐸
𝑘𝐵𝑇−1)
is the spectral photon flux of
the black body radiation and the temperature T is 23 °C (temperature of the EL measurements).
We recalibrated the absorptance with the above bandgap IPCE at 760 nm (1.63 eV) from Fig. 4C
(IPCE (1.63 eV) = 87.7%). This yields the absorptance spectrum as shown in fig. S20. The
exponential fit between 1.4 and 1.5 eV results in the Urbach energy 𝐸𝑢 = 13.9 meV. From 𝑎(𝐸) we calculated the emitted photon flux in thermal equilibrium 𝐽𝑒𝑚,0 = 𝑒 ∫ 𝑎(𝐸)𝛷𝐵𝐵(𝐸)𝑑𝐸 and
from this the radiative limit open-circuit voltage 𝑉oc,rad = 𝑘𝐵𝑇 𝑒⁄ ln(𝐽𝑝ℎ 𝐽𝑒𝑚,0 + 1⁄ ) = 1.254 V ,
where 𝐽𝑝ℎ = 25 mA/cm2 is the short circuit current under one sun illumination. For this calculation
we used the temperature T = 20.1°C, which is the temperature of the device with the highest Voc
(1.19 V) measured under cooling air flow (Fig. 4D). In fig. S21, A and B, we showed how the
temperature affected the calculated Urbach energy and 𝑉oc,rad, respectively. The Urbach energy determined from the EL as explained above varies from 13.7 meV at 15 °C to 14.1 meV at 30 °C,
which demonstrates that it has a very small temperature effect. As for the temperature effect on
𝑉oc,rad, we calculated 𝑉oc,rad = 1.259 V at 15 °C and 𝑉oc,rad = 1.245 V at 30 °C, i.e. 𝑉oc,rad changes 1 mV/°C. The expected 𝑉oc,exp = 𝑉oc,rad + ∆𝑉oc [ ∆𝑉oc = 𝑘𝑇 𝑞⁄ ln(𝜂𝑒𝑥𝑡) ] has a temperature
dependence as shown in fig. S21C.
We did our J-V measurements under two conditions: 20. 1 °C (for air flow cooled samples) and
25 °C (for non-air flow cooled samples). The measured Voc is 1.19 V at 20.1 °C and 1.18 V at 25
°C without using a mask, and a relevant 𝑉oc,exp is calculated to be 1.185 V and 1.179 V, and ∆𝑉𝑜𝑐
is 69.0 mV and 70.2 mV, respectively. We note that the measured EQEEL is underestimated, as a
considerable number of emitted photons are trapped inside the glass layer. Thus, the difference
between the measured and predicted values could be due to the inaccuracy of EQEEL
measurements.
Lastly, we determined the measured Voc of 1.18 ± 0.005 V for the mask-free conditions at a
temperature of 25 °C (error is given from a 5 °C temperature range).
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Fig. S1. XRD patterns of FAPbI3 perovskite films after MASCN vapor treatment for
different time from 0 to 100 s.
5 10 15 20 25 30 35 40 45 50 55 60 65
100 seconds treatment
10 seconds treatment
5 seconds treatment
2 seconds treatment
untreated
Norm
alis
ed I
nte
nsi
ty
2q (o)
d
d
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Fig. S2. 2D-GIXRD measurements of the FAPbI3 films. 2D-GIXRD patterns collected at X-ray
incident angles of (a) 0.05°, (b) 0.10° and (c) 0.40° from the reference FAPbI3 perovskite film.
2D-GIXRD patterns collected at X-ray incident angles of (d) 0.05°, (e) 0.10° and (f) 0.40° from
the MASCN vapor-treated FAPbI3 perovskite film. GIXRD spectra around the perovskite (001)
diffraction peaks at incident angles of 0.05°, 0.10° and 0.40° for (g) the MASCN-vapor treated
FAPbI3 perovskite films and (h) the reference FAPbI3 perovskite films. GIXRD spectra around the
perovskite (001) diffraction peaks at incident angles of (i) 0.05° and (j) 0.40° for both the MASCN
vapor-treated and reference FAPbI3 perovskite films.
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Fig. S3. Characterization of the FAPbI3 films. Atomic force microscopy (AFM) images of (a)
reference FAPbI3 film and (b) MASCN vapor-treated FAPbI3 film. Top-view SEM images of δ-
phase FAPbI3 perovskite films before vapor treatment: (c) scale bar is 200 nm and (d) scale bar is
1 µm.
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Fig. S4. ToF-SIMS depth profiles. (a) MA+ and FA+ contents of the vapor-treated FAPbI3, 1 mol
% MA+-doped FAPbI3 reference and background signal from pure FAPbI3 reference films. (b)
PbI2- and SCN- contents of the vapor-treated FAPbI3 film. The sputtering time of 100 s corresponds
to a distance of ~100 nm.
100
101
102
103
104
0 20 40 60 80 100
100
101
102
103
104[PbI2]
-
Inte
nsity (
counts
)
13FA+ ([13CH(NH2)2]+) (vapor-treated FAPbI3)
Perovskite
background signal from pure FAPbI3 reference
MA+ ([CH3NH3]+) (vapor-treated FAPbI3)
MA+ ([CH3NH3]+) (1 mol % MA+ in FAPbI3 reference)
(vapor-treated FAPbI3)
(vapor-treated FAPbI3)
(vapor-treated FAPbI3)[SCN]-
Inte
nsity (
counts
)
Sputter time (s)
[34SCN]-
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Fig. S5. 1H-1H spin diffusion measurements at 21.1 T, 20 kHz MAS and 298 K at 1 s of
mixing time.
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Fig. S6. Simulation set-up: δ-FAPbI3 with MA+ and SCN- on top. This image was generated
with Visual Molecular Dynamics (VMD). Pb-I octahedra are shown with golden color with iodide
as orange balls at the corners of the octahedra. FA+, MA+, and SCN- ions are shown with ball and
sticks representation. Nitrogen is dark blue, carbon is light blue, hydrogen is white, and sulfur is
yellow.
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Fig. S7. Top view of the adsorption of SCN- ions on top of δ-FAPbI3. (a) Top view of the
simulations. (b) A zoomed-in version of a small part of the top view to clearly show the adsorption
of SCN- ions on top. These images were generated with VMD. The color coding is the same as in
fig. S6.
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Fig. S8. Configuration for the δ-FAPbI3 with SCN- on top. (a) The starting configuration (at
t=0) and (b) the configuration at t = ~10 ps for the δ-FAPbI3 with SCN- on top. We show the
dimensions of the supercell to display the empty space used to treat the SCN- ions as vapor between
periodic slabs. Pb2+ ions and octahedron are shown with golden colour with iodide as pink balls.
FA+ and SCN- ions are shown with ball and sticks representation. The color coding is the same as
in Fig. S6.
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Fig. S9. The formation of Pb-I-SCN octahedra and the radial distribution. (a) The formation
of Pb-I-SCN octahedral during ab-initio MD. Pb2+ ions and octahedron are shown with golden
colour with iodide as orange balls. FA+, MA+, and SCN- ions are shown with ball and sticks
representation. The color coding is the same as in fig. S6. (a). (b)The radial distribution function
g(r) between the sulfur atoms of SCN- and Pb2+ over the full ab-initio MD trajectory.
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Fig. S10. A zoomed-in view of the final configuration of corner-sharing structures on the
interface. This image was generated with VMD. The color coding is the same as in fig. S6.
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Fig. S11. Illustration of a possible phase transition path induced by SCN- anions. (a) δ-phase
FAPbI3 structure. The mixtures of δ and α-phases of FAPbI3 with the increasing number of corner-
sharing structures from (b) to (e). (f) α-phase FAPbI3 structure. SCN- ions are adsorbed on the top
of the respective structures. Pb2+ octahedra are portrayed with light blue colour with iodide as pink
balls on corners. FA+ and SCN- ions are represented with ball and sticks representation. The color
coding is the same as in fig. S6. All the images were generated with the VESTA software.
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Fig. S12. Characterization of the FASCN vapor-treated FAPbI3 films. (a) XRD patterns of
the reference and FASCN vapor-treated FAPbI3 films annealed at 100 °C (inserted are the
pictures of corresponding FAPbI3 films after annealing). (b) J-V curve of one FASCN-treated
FAPbI3-based solar cell device.
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Fig. S13. A possible transition pathway and corresponding activation barrier: Illustration of
a possible phase transition pathway between δ and α-phases FAPbI3. Each point on the energy
plot represent a different optimized structure along the path. A Gaussian fit of these points is
included as guide to the eyes. For better visualization of the pathway, we have illustrated some of
the intermediary phases. Pb-I octahedra are represented with light green colour with iodide on
corners with pink balls. FA+ cations are shown with ball and sticks representation. The color coding
is the same as in fig. S6. All images were generated with the VESTA software.
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Fig. S14. Cross sectional scanning electron microscopy (SEM) image of a complete solar
cell device using glass/ITO/SnO2/FAPbI3/Spiro-OMeTAD/Au structure. The thicknesses of
SnO2, FAPbI3, Spiro-OMeTAD are about 20 nm, 480 nm and 200 nm, respectively.
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Fig. S15. Statistic distributions of PV metrics, including (a) Jsc, (b) Voc, (c) FF and (d) PCE
for the MASCN vapor-treated FAPbI3 based PSCs.
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Fig. S16. PV performance of the vapor-treated FAPbI3 PSCs. J-V curves measured for one
stressed FAPbI3-based PSC (a) in IMT and (b) in our lab. Measurements under MPP tracking
conditions for one stressed FAPbI3-based PSC (c) in IMT and (d) in our lab.
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Fig. S17. J-V curves of one reference FAPbI3-based PSC under both forward and reverse
scan directions.
0.0 0.2 0.4 0.6 0.8 1.0 1.2
0
5
10
15
20
25
PCE = 16.31%
Forward scan
Reverse scan
Cu
rren
t d
ensi
ty (
mA
/cm
2)
Voltage (V)
PCE = 17.95%
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Fig. S18. Steady state power output for one of the MASCN-treated FAPbI3-based PSCs at
MPP condition under one sun condition for 60 s.
0 10 20 30 40 50 60
0
5
10
15
20
25
PC
E (
%)
Time (s)
MPP tracking
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Fig. S19. Voc as a function of time for 350 s for one of the MASCN-treated FAPbI3-based
PSCs under 0.9 sun illumination at room temperature.
0 50 100 150 200 250 300 350
1.00
1.04
1.08
1.12
1.16
VOC
Vo
lta
ge
(V
)
Time (s)
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Fig. S20. Absorptance and exponential fit to determine the Urbach energy. For comparison
the EL spectrum from Fig. 4E and the spectral photon flux of the black body radiation at 23 °C
are shown.
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Fig. S21. Theoretical calculations. (a) Urbach energy Eu , (b) radiative limit Voc , and (c) expected
Voc as a function of temperature calculated from the EL curve shown in fig. S20. The stars in (c)
indicate the Voc of measured devices.
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Fig. S22. Tauc plot resulting in a 1.52 eV bandgap for the MASCN-treated FAPbI3 films.
1.46 1.48 1.50 1.52 1.54 1.56 1.58 1.60 1.62 1.64
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
(ahn)2
Energy (hn)
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Fig. S23. TRPL measurements of the reference and the MASCN vapor-treated FAPbI3
films.
0 1000 2000 3000
10-3
10-2
10-1
100
Re
lative
in
ten
sity (
a.u
.)
Time (ns)
Treated FAPbI3 tavg=299.3 ns
Reference FAPbI3 tavg=79.8 ns
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Fig. S24. Wall-plug efficiency of the MASCN-treated FAPbI3-based PSC devices as a
function of bias voltage from 0 to 2V.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0
2
4
6
8
Wal
l-plu
g e
ffic
iency
(%
)
Voltage (V)
-
31
Fig. S25. EQEEL of the MASCN-treated FAPbI3-based PSC devices as a function of the
current density from 0 to 300 mA/cm2.
0 50 100 150 200 250 300
0
2
4
6
8
10
EQ
EE
L (
%)
Current density (mA/cm2)
-
32
Fig. S26. XRD patterns of the FAPbI3 films. (a) MASCN-treated FAPbI3 films annealed at 85
℃ under N2 for 100, 300 and 500 hours. (b) Reference FAPbI3 films annealed at 85 ℃ under N2 for 0 and 500 hours.
-
33
Fig. S27. J-V curves of the fresh FAPbI3-based PSCs and the FAPbI3-based PSCs after
2500 hours storage in a dry box.
0.0 0.2 0.4 0.6 0.8 1.0 1.2
0
5
10
15
20
25
Cu
rren
t d
ensi
ty (
mA
/cm
2)
Voltage (V)
Reverse scan of the device after 2500 hours
Forward scan of the device after 2500 hours
Reverse scan of the initial device
Forward scan of the initial device
-
34
Movie S1. The behavior of SCN- ions after addition of MASCN on top of δ-FAPbI3. We show
SCN- ions in balls and sticks representation: sulfur as yellow, carbon as light and nitrogen as blue
colored balls. MA+ ions are omitted for the sake for clarity. The Pb-I octahedra of δ-FAPbI3 are
shown with light-grey color with iodide as pink colored balls. FA+ ions are not shown for better
visualization.
Movie S2. A top view of the simulation showing that many SCN- ions get adsorbed on the
interface by replacing the iodide ions.
Movie S3. A full simulation of adding MASCN on top of δ-FAPbI3. Pb-I octahedra in δ-FAPbI3
are shown with golden color with iodide on corners as pink balls. FA+ ions shown with light blue
color, can be seen around face-sharing Pb-I octahedra. MA+ and SCN- ions are shown with balls
and sticks representation: sulfur with yellow color, carbon with light blue color, nitrogen with blue
color and hydrogen with white color.
Movie S4. Behavior of MA+ ions after addition of MASCN on top of δ-FAPbI3. We show MA+
ions in green color, SCN- ions are omitted for the sake of clarity. The Pb-I octahedra of δ-FAPbI3
are shown with light-grey color with iodide as pink colored balls. FA+ ions are not shown to better
visualize the diffusion of MA+ ions.
Movie S5. The transformation of face-sharing octahedra to corner-sharing octahedra on the
top surface layer of δ-FAPbI3. Here we show a part of the simulation box, mainly to clearly
visualize the transformation by the strongly coordinated SCN- ions on the top surface layer. Pb-I
octahedra are represented in golden color with iodide in corners as pink balls. SCN- ions are shown
with balls and sticks configuration: sulfur with yellow color, carbon with light blue color, and
nitrogen atoms with blue balls. SCN- coordinating octahedra are shown with red color for better
view.
Movie S6. The formation of different kinds of corner-sharing structures on top of δ-FAPbI3
after loading the MASCN.
Movie S7. The formation of polytypes through the interaction with SCN- ions.
-
35
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