Interface Engineering of Perovskite Solar Cells With PEO For Improved Performance
Interface Engineering of Perovskite Solar Cells With PEO For Improved Performance
Materials Chemistry A
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decreased. Compared with devices with TiOx only, devices based on the modied ETL gave a nearly 15%
enhancement to the overall conversion eciency, with both Voc and Jsc improved. Further studies
DOI: 10.1039/c5ta00407a
showed that the improved performance could mainly be attributed to the better retardation of back
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recombination and the enhanced electron collection eciency by means of the PEO thin layer modication.
1. Introduction
Organicinorganic hybrid perovskite solar cells have been a
quite hot research topic recently, due to their rapid and
improved power conversion eciency (PCE).14 The latest record
certied by the National Renewable Energy Laboratory (NREL)
was 20.1%, which is very close to its theoretical PCE. With the
increase in the PCE, also new structures with this kind of solar
cell have been developed. At the beginning, a classical structure
of dye-sensitized solar cells was adopted, with mesoporous TiO2
as the electron collection and transport layer,5,6 but now devices
with insulating nanoparticles (such as Al2O3, ZrO2) as scaolds
have also been reported and have achieved great success.7,8
Planar structured perovskite solar cells have also been widely
researched and have given quite good results.9,10
For most of the structures, a thin layer of TiO2 or ZnO is
commonly used on a transparent conductive electrode (usually
FTO or ITO) as the electron transport layer (ETL). Matching the
energy level could prevent holes formed in the perovskite or
hole transport layer (HTL) from reaching the conductive electrode, which would otherwise lead to a back recombination and
reduced short-circuit current. Optimization of this layer is an
eective means to further improve the performance of the solar
cells. Snaith et al. developed a low temperature route for
b
Institute of Modern Optics & State Key Laboratory for Articial Microstructure and
Mesoscopic Physics, School of Physics, Peking University, Beijing, P. R. China
2.
2.1
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Experimental section
Materials and reagents
Device fabrication
TiOx ETL was fabricated on FTO glass through the atomic layer
deposition (ALD) method. The perovskite solar cells were fabricated using a similar process to Snaith's group, with the optimized parameters, whereby a thin layer of Al2O3 scaold was
spin-coated on the substrate at a rotation speed of 6000 rpm for
60 s, then dried at 150 C on a hotplate for 30 min. The perovskite
layer was prepared by spin-coating from a homogeneous 40 wt%
precursor solution (PbCl2 : MAI 1 : 3, in DMF) and annealed at
100 C for 90 min. Aer cooling down to room temperature, the
HTL layer was spin-coated on top with a spinning speed of
2500 rpm, for 60 s. Finally, a 50 nm thick gold electrode was
deposited by thermal evaporation through a shadow mask. The
active area of the studied devices was 10 mm2. For the devices
with PEO modication, a solution of PEO/acetonitrile was spincoated on to the ALD-TiOx layer at 5000 rpm for 60 s and then
dried at 60 C for 15 min to remove the residual solvent.
2.3
Characterizations
3.
3.1
Fig. 1 Atomic force microscopy images of (a) FTO/TiOx and (b) FTO/
TiOx/PEO.
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3.2
Photovoltaic performances
Fig. 3 XPS focus on the (a) Ti2p and (b) O1s peaks for FTO/TiOx and
FTO/TiOx/PEO lms. (c) UPS spectra of TiOx and TiOx/PEO lms. The
light source of UPS was a He1 discharge lamp (hn 21.2 eV).
Control
1 mg mL1
2.5 mg mL1
5 mg mL1
Control
(average s.d.)a
2.5 mg mL1
(average s.d.)a
Voc [V]
PCE [%]
1.00
1.01
1.02
1.01
1.03 0.03
17.9
18.6
20.7
18.7
17.1 1.1
11.8
12.5
13.8
11.4
10.8 0.90
0.66
0.67
0.65
0.60
0.61 0.03
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Fig. 6 (a) UV-vis absorption of the perovskite active layers for solar
cells; (b) PL decay spectra of lms: FTO/TiOx/MAPbIxCl3x (black
curve) and FTO/TiOx/PEO/MAPbIxCl3x (red curve).
a lot aer spinning a layer of PEO, so the active layer should not
be aected by the inserted PEO layer. The 4inj was positively
related to the ETL's electron extraction ability from the perovskite layer, which could be measured by the photoluminescence
spectroscopy (PL) decay.22 As shown in Fig. 6(b), with a thin layer
of PEO, the PL quenching was slightly reduced, indicating it was
a little hard for the electrons to inject into the hole-blocking
layer. This suggested that the PEO reduced the 4inj mildly due to
its insulating property. This was also conrmed by the
enhanced steady state PL for the TiOx/PEO/perovskite sample,
as shown in Fig. S7. Now that the LHE remains constant and
the 4inj is even a little decreased, the enhancement of IPCE
should contribute to the improved hcol.
The charge collection eciency (hcol) cumulatively takes into
account the transport and recombination dynamics and could
be dened by the following equation:23
hcol transport rate/(transport rate + recombination rate)
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curves. Anyway, both the dark current and the EIS results
indicated that inside the devices, the back recombination was
retarded with a thin layer of PEO, leading to a higher hcol.
Thus, out of the three parameters dening the IPCE, LHE
remained constant and 4inj decreased a little upon addition of
the PEO modication overlayer on the TiOx blocking layer. In
contrast, the appreciable gain in charge collection eciency
oset the loss in injection eciency and served to explain the
enhanced IPCE and Jsc observed for devices with a PEO modication layer.
4. Conclusions
In summary, we introduced a PEO thin layer into perovskite
solar cells for surface engineering of the electron transport
layer. This thin layer was uniformly coated on top of the TiOx,
without changing the ETL's morphology, transparency or
hydrophilicity. Due to the dipole formed at the interface, the
work function of the ETL decreased with a thin layer of PEO.
Compared with devices with TiOx only, devices based on the
modied ETL gave a nearly 15% enhancement on the overall
conversion eciency, with both Voc and Jsc improved too. This
could mainly be attributed to the better retardation of the back
recombination and the enhanced electron collection eciency
by means of the PEO thin modication layer. Our results
suggest that interface engineering could be an eective
approach to further improve the performance of the perovskite
solar cells.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China under Grant no. 51273104 and the
National Natural Science Foundation of China under Grant no.
91433205.
Fig. 7 (a) JV characteristics of solar cells based on TiOx and optimized TiOx/PEO ETL tested in the dark; (b) EIS spectra of solar cells
based on TiOx and optimized TiOx/PEO ETL tested in the dark with a
0.9 V bias voltage.
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