Cheng 2015
Cheng 2015
Cheng 2015
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S. Meyer, Y. Dkhissi, K. Weber, J. Pringle, U. Bach and L. Spiccia, J. Mater. Chem. A, 2015, DOI:
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DOI: 10.1039/C5TA00358J
DOI: 10.1039/x0xx00000x The stability of encapsulated planar-structured CH3 NH3 PbI 3 (MAPbI 3) perovskite solar cells
(PSCs) was investigated under various simulated environmental conditions. The tests were
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performed under approximately one sun (100 mW/cm2) illumination, varying temperature (up
to 85 °C cell temperature) and humidity (up to 80%). The application of advanced sealing
techniques improved the device stability, but all devices showed significant degradation after
prolonged aging at high temperature and humidity. The degradation mechanism was studied by
post-mortem analysis of the disassembled cells using SEM and XRD. This revealed that the
degradation was mainly due to the decomposition of MAPbI 3, as a result of reaction with H2O,
and the subsequent reaction of hydroiodic acid, formed during MAPbI 3 decomposition, with
the silver back contact electrode layer.
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corroded by 4-tert-butylpyridine (4-tBP) which is an important simulated light intensity. The solar cells were dismantled after
additive in the Spiro-OMeTAD hole transporting material.19 the stability tests to investigate the degradation pathways.
The corrosion was proposed to occur because 4-tBP was able to
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B1), and is specifically designed for OLEDs and has a low The surface and cross sectional SEM images were recorded
water vapour transmission rate of around 3 × 10-4 g/m per day with a FEI Nova dual beam, focused ion beam (FIB), SEM
according to the manufacturer. The sealing of the devices was instrument using 5kV acceleration voltage. Prior to ion beam
both the device fabrication and encapsulation procedures were 10, with a scan rate of 1° min−1 and a step size of 0.02°.
carried out in an inert atmosphere,27 and/or a reaction of the
perovskite material with vapours outgassing from the UV Environmental Stability Testing Conditions
epoxy during the UV-curing procedure. Thus, the stability Stability testing was conducted using an ATLAS
studies were performed on devices with an initial average PCE Environmental Chamber (SC 340 MHG), which enables a
of around 12%. controlled temperature range of -20 °C to 100 °C, relative
humidity between 0% to 80% and uses a 1200 W metal halide
lamp that gives approximately one sun illumination constantly
during the entire testing period. The output of the halide lamp
was regulated to yield short circuit currents that are comparable
to the values measured using a Xe solar simulator for a standard
Si solar cell. The solar cells were kept inside the chamber at
open circuit, with a 0.16 cm2 circular aperture on top to define
the illuminated area. A K-type thermocouple was directly
attached to one solar cell of each batch to monitor the actual
cell temperature during testing. During illumination, the actual
cell temperature was found to be approximately 30 °C higher
than the environmental temperature inside the chamber. For the
ease and clarity of discussion in the following sections, the
temperatures are always presented as “environmental
temperature (actual cell temperature)”, e.g., 55 °C (85 °C). The
Figure 2. Schematic cross-section of the perovskite solar cells sealed according to
technique A (top) and B (bottom). environmental temperature, actual cell temperature and
photovoltaic performances of the devices (Voc, Jsc, FF and PCE)
were continuously monitored and recorded every 5 minutes
using an automated external I-V recording instrument (National
Instruments PXIe-1078).
The stability testing conditions were designed to closely follow
a consensus of the stability testing protocols for organic
photovoltaic materials and devices.28 Cells sealed by method A
were tested under three different environmental conditions:
i. constant temperature -20 °C (10 °C), 0% relative
humidity, one sun continuous illumination;
ii. constant temperature 55 °C (85 °C), 10% relative
humidity, one sun continuous illumination;
iii. constant temperature 55 °C (85 °C), 80% relative
humidity, one sun continuous illumination.
Cells sealed by method B were then tested and compared with
cells sealed by method A under environmental condition (iii).
Further stability testing of cells sealed by method B under
environmental condition (iv) was then conducted for over 500
hours:
iv. constant temperature 55 °C (85 °C), 50% relative
Figure 3. Photographs of solar cells sealed by method A (top) and B (bottom). humidity, one sun continuous illumination.
Scanning Electron Microscopy (SEM) images and X-ray Results and discussion
diffraction (XRD) patterns
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Device Stability
The stability of the CH3NH3PbI3 perovskite solar cells sealed by
method A was examined under three different environmental
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would get significantly hotter than the covered area in the rest
of the cell. The severer damage observed in the exposed
circular area may be a result of combined thermal degradation
Figure 5. Front and back photographs of a perovskite solar cell sealed by method
A after 120 h illumination at approximately one sun, 55 °C (85 °C) and 80%
relative humidity.
Figure 7. Photographs of a perovskite solar cell sealed with method B after 500 h
Additionally, a 500 h long-term test under environmental of illumination at 55 °C (85 °C) and 50 % humidity (conditions (iv)). The
condition (iv) was conducted using a new batch of three cells encapsulating cover glass was removed for a better view.
sealed by method B. All of these devices were still working
after the test, but showed significant degradation, maintaining After removal of the glass cover, cross-sectional FIB-SEM
only less than 5% of their initial efficiency. All photovoltaic images of the degraded cell were taken (Figures 8 and 9).
parameters were reduced during aging, probably because of the Compared to the new cells, a number of degradation features in
gradual decomposition of the MAPbI3 layer. The decrease in the aged cell were evident: (a) damage and fragmentation of the
FF could also be arising from the gradual increase of the total silver layer; (b) voids formed in the Spiro-OMeTAD layer; (c)
series resistance of the cell, as shown in Figure 6, which was voids formed in the perovskite layer and detachment of the
also measured in-situ during the aging test. A detailed post- perovskite layer from the TiO2 layer; (d) formation of new
mortem analysis of the degraded cells was conducted and the particles containing elements of high atomic numbers (brighter
results are discussed in the following sections. contrast in the SEM image) in the perovskite layer. Further
analyses of the degraded devices are presented in the following
sections.
Figure 6. Gradual increase of the total series resistance of the cells tested at
constant temperature (55 °C (85 °C)) and humidity (50%) under continuous one
sun illumination (environmental condition (iv)). Resistance values from three
devices were averaged and the error bars show the standard deviation.
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Figure 10. Design of samples with three different structures used for the aging
tests; (A) Sample DA without a perovskite layer; (B) Sample DB without a Spiro-
OMeTAD layer; (C) Sample DC with only the perovskite layer, all on a TiO2
blocking layer coated FTO glass. All samples were encapsulated using the sealing
method B illustrated in Figure 2.
Figure 8. Cross-sectional FIB-SEM images of a new cell (A) and different areas of In the perovskite free sample (DA) the microstructures of the
the aged cell (B-D) at constant temperature (55 °C (85 °C)) and humidity (50%) silver, Spiro-OMeTAD, TiO2 and FTO layers in both the new
for 500 h. Degradation features are marked as follows: voids in the Spiro-
and aged cells showed almost no difference in the cross
OMeTAD layer (□); voids in the perovskite layer and detachment of the
perovskite layer from the TiO2 layer (Δ); damaged and discontinuous silver layer sectional images after the aging test (Figure 11 B and C). In
(○) and formation of particles with higher atomic numbers, likely PbI2 (◊). addition, there was no evidence of degradation of the top Ag
layer, from comparison of Figure 11A and Figure 9A. This
indicated that Spiro-OMeTAD was stable in contact with silver
and TiO2 under condition (iv) (55 °C (85 °C), 50% humidity
and 500 h). Thus, it can be concluded that the damages to the
silver layer and the formation of voids in the Spiro-OMeTAD
layer in the aged solar cell (Figures 8) were mainly associated
with the degradation of the perovskite material at high
temperature and humidity.
Figure 9. SEM images of the surface of the silver layer in a new (A) and an aged
(B) perovskite solar cell that was tested at constant temperature (55 °C (85 °C))
and humidity (50%) for 500 h.
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aging test (Figures 12 B and C). More precisely, the FIB cross-
sectional SEM images in Figures 12 D and E show that the
perovskite layer has changed dramatically. That is, a significant
Figure 13. Powder XRD patterns of (A) new Ag coated on TiO2/FTO/glass; (B)
new, (C) and (D) aged sample DB (Ag/perovskite/TiO2/FTO/glass) at 55 °C (85 °C),
50% humidity; (Δ) peaks from the CH3NH3PbI3 perovskite phase.
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*
showed good performance at room temperature and zero Corresponding authors. Email: yibing.cheng@monash.edu,
humidity, but degraded at high temperature and humidity. leone.spiccia@moansh.edu.
Improved stability was demonstrated by adopting a sealing
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the formation of voids in the perovskite layer, plus detachment 7. Q. Chen, H. Zhou, Z. Hong, S. Luo, H.-S. Duan, H.-H. Wang, Y. Liu,
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