Nanoscale Degradation Mechanism of Mixed Cation Perovskite

under Humidity and Light Revealed by Peak Force Infrared Microscopy

Kevin Ho, and Gilbert C. Walker*
Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada

After 17 - 20 hrs, the

ABSTRACT Degradation pathways
This degradation pathway summarizes the findings from the degradation by
morphology and
X-ray diffraction (XRD)

Light and water are well known factors that can cause degradation to organic PFIR intensity does α α-CsFAPbI3 δ δ-FAPbI3
light and high humidity. δ0-CsPbI3 Time
lead halide perovskites, which hinders their commercial applications. Here, we not change. O
* PbI2
studied the degradation mechanism of FA0.85Cs0.15PbI3 using peak force infrared δ-FAPbI3 δ 34 hr After 32 hrs, δ-FAPbI is
microscopy, which enables subdiffractional spatial identification of the
At 0 hr, the surface is FAI When exposed to light
δ αδα α
3
still present in the XRD,
homogenous from FAI or high humidity alone,

CsFAPbI3
O O
formamidinium (FA) cation and allows us to probe the degradation mechanism
of individual grains. We found that upon exposure to light or water alone, no
both the atomic force I2 no degradation occured δ
but from PFIR, the the
26 hr large grains shrank. This
microscopy (AFM) and PbI2 PbI2 during this time. *O δ
significant change in the spatial distribution of FA and no pure inorganic α δ α α α difference arised because
decomposition product was observed. However, upon exposure to both light
PFIR. Pb O
XRD samples a very large
and high humidity, we found that FA0.85Cs0.15PbI3 degrades through a multistep δ0-CsPbI3 12 δ *O area (mm2) but PFIR
pathway. First, α-FA0.85Cs0.15PbI3 decays to δo-CsPbI3, δ-FAPbI3, and PbI2 and the CsI V
O α α δα α images only the central
distribution of the FA cation became increasingly inhomogeneous. Second, the Exposure to spot in the wafer (μm2).
δ
A
organic cations are lost and PbI2 further photodecomposes. 17 hr

Intensity (a.u.)
low humidity *α

PFIR
1 δα α
and light Large grains formed rapidly 400 O α
from 8 - 13 hrs. The large nm δ O
grains show a large increase *α δ α α 13 hr
INTRODUCTION in the PFIR signal. O α

AFM
0 hr 17 hr -400 δ 9 hr
Perovskites are a promising materials for solar cell applications, but suffer
rapid degradation due to various factors such as heat, light, and humidity. XRD shows the formation of 12 O
*α α δ α α
8 hr
δ-FAPbI3 during this time. V After 6 hrs, δ-FAPbI3, and
α 6 hr
The degradation pathways of mixed cation perovskites have been less well Exposure to δ *α PbI2 began to form.
understood. Futhermore, the degradation have not been well studied at the B high humidity
The large grains correspond O αδ α

PFIR
length scale of the individual grains. to the formation of δ-FAPbI3. 1 α α
in the dark 400
nm α α The characterisitc peaks
0 hr for a perovskite are
In this experiment, we studied the degradation of a mixed cation perovskite,
shown at 0 hr.
focusing on the chemical and structural change to the individual grains as 5 10 15 20 25 30 35
-400
AFM

the degradation occured. 0 hr 20 hr 2θ (deg.)

To achieve this, we used peak force infrared microscopy. 12

V
The large grains shrank
and the PFIR intensity
decreased as the volatile
PFIR

organic component in
C δ-FAPbI3 evaportaed. 1
400
nm
Exposure to
high humidity
and light
AFM

0 hr 5 hr 8 hr 9 hr 13 hr 17 hr 28 hr -400 Time

α-CsFAPbI3
CsPbI3 CsPbI3
PbI2 PbI2
δ-FAPbI3 δ-FAPbI3 CONCLUSION
o PFIR was used as a novel technique to study the degradation of
At 0 hr, the sample is perovskites at the nanoscale.
homogenous in both Time-of-flight secondary o When exposed to high humidity or light alone, degradation of FA0.85Cs0.15PbI3
MATERIALS and METHODS The needles do not show
Cs
240

I
AFM and PFIR. ion mass spectrometry was not observed under 20 hr. With simultaneous exposure to light and high
any PFIR absorption at
humdity, the degradation occurred in a two step process.
a. u.

(TOF-SIMS) shows a 1712 cm-1.

The mixed cation perovksite, FA0.85Cs0.15PbI3 was used in the degradation studies. o First, FA0.85Cs0.15PbI3 phase separated into CsPbI3 needles and FAPbI3 as large
400 9 hr After 5 hrs of simultaneous strong signal in the Cs 400
0

12 nm
nm V
and I channel on the
-400 grains.
exposure to light and high 12 V

needles. 0 o PbI2 was formed as depressions, as volatile FAI evaporated.

humidity, needles and 9 hr 13 hr
1 o Second, large grains disappeared, and PbI2 was converted to Pb and I2.
-400 depressions were formed.
*data from another sample
N2

PbI2, CsI, FAI

in DMF/DMSO
Static spin coat
onto a ITO/
Thermal anneal:
150 C, 10 min Peak Force Infrared Microscopy (PFIR) The needles are ACKNOWLEDGEMENTS
Pb solution glass substrate The depression does not identified as CsPbI3.
under N2 have PFIR absorption at 1 2 3
I lase
r
Cs 1712 cm-1, therefore, it does
formamidinium (FA) not contain the FA cation.
H Photodegradation
Imaged in the dark, low humidity: light source
<20% R.H., 22 C. 20% R.H.
The depressions are PbI2. Laser is focused onto The sample thermal expands The deflection can be
Intensity: the tip and the sample. after absorbing the light. measured as a function of
+
H2N NH2 Peak Force tapping mode high humidity: 10 mW/cm2
with Bruker InspireTM The tip is deflected from the the wavenumber or
85% R.H. wavelength range: thermal expansion. spatial position.
500 - 1200 nm