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Cite this: Nanoscale, 2015, 7, 896

Received 10th October 2014,
Accepted 15th November 2014
DOI: 10.1039/c4nr05975a
www.rsc.org/nanoscale

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Eciency enhancement of planar perovskite solar

cells by adding zwitterion/LiF double interlayers
for electron collection
Kuan Sun, Jingjing Chang, Furkan Halis Isikgor, Pengcheng Li and
Jianyong Ouyang*

Double interlayers consisting of a zwitterionic small molecule layer

and a LiF layer were introduced between the electron transport
layer and the cathode of perovskite solar cells. The double interlayers improve the photovoltaic eciency to 13.2%, which is
higher than that of control devices without the double interlayer
(9.2%) or with LiF (11.0%) or rhodamine 101 zwitterion (12.1%)
alone.

Since the reports on solar cells with organicinorganic hybrid

perovskite materials with high power conversion eciency in
2012,1,2 organolead halide based perovskite solar cells (PSCs)
have attracted considerable attention, owing to their simple
fabrication process, low materials and fabrication costs and
high power conversion eciencies (PCEs). Two types of device
structures have been developed: one type of devices has a layer
of scaold metal oxide, such as TiO2 or Al2O3 on indium tin
oxide (ITO) or fluorine doped tin oxide (FTO).36 The porous
metal oxide layer can restrict the growth of the perovskite crystals, while large perovskite crystals can lead to large leakage
current and poor photovoltaic eciency.7 Usually, a hightemperature step is needed for the preparation of the scaold
metal oxide layer, and the morphology of the scaold metal
oxide layer strongly aects the photovoltaic performance of the
devices. The other type of perovskite solar cells has a planar
structure without the scaold metal oxide layer.815 The holes
and electrons generated in the perovskite layer transport
through the hole-collection and electron-collection layers,
respectively, to the two electrodes. The fabrication of planar
perovskite solar cells with organic materials for electron and
hole transport does not require a high temperature step.
Materials, which cannot sustain high temperatures like plastics, can thus be used in planar perovskite solar cells. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:

Department of Materials Science & Engineering, National University of Singapore,

7 Engineering Drive 1, Singapore 117574. E-mail: mseoj@nus.edu.sg;
Fax: +65 6776 3604; Tel: +65 6516 1472
Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05975a
These authors contributed equally to this work.

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PSS) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are

the popular materials for the hole and electron transport
layers, respectively, because they can be processed by solution
coating and form good physical and electronic contacts with
the perovskite layer. Nevertheless, the energy levels of PCBM
do not match well with the top metal electrode, such as Ag. As
known from organic solar cells, the interfaces between the
active layer and the electrodes significantly aect the light-toelectricity conversion eciency.1619 Hence, the electrons
cannot be eciently collected at the cathode of PSCs due to
the energy mismatch between PCBM and cathode. Interfacial
materials including bathocuproine (BCP),20,21 LiF,22 solution
deposited TiOx,23 tris(2,4,6-trimethyl-3-( pyridine-3-yl)phenyl)borane (3TPYMB),24 or polyelectrolyte,25 were used between
the PCBM layer and the top cathode to improve the electron
collection. Wang et al. also used a layer of C60 and a layer of
BCP between PCBM and the top metal electrode.20 The C60
layer passivates the defects of the perovskite layer, while the
BCP layer can block hole transport and facilitate electron collection. Double interfacial layers have shown a better performance than a single interlayer in organic solar cells due to more
ecient charge extraction or suppression of trap-assisted
recombination.26,27
In this work, we have investigated the application of rhodamine 101 that is a zwitterion (chemical structure shown in
Fig. 1(a)) as the electron-collection interfacial layer and rhodamine

Fig. 1 (a) Chemical structure of rhodamine 101, and (b) device architecture of perovskite solar cells employing rhodamine 101/LiF double
interlayers.

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101/LiF as double interlayers between PCBM and the Ag electrode of PSCs. As observed on organic solar cells, zwitterions
that have the positive and negative charges on the same molecule can lower the work function of electrodes by the formation of surface dipoles.28,29 The rhodamine 101 layer can be
deposited via solution processing without aecting the bottom
layers. The presence of the rhodamine 101 layer can increase
the PCE from 9.2% to 12.1%, which is higher than the PCE
(11.0%) of the PSC with a LiF layer thermally deposited. The
PCE is further improved to 13.2% when double interlayers of
rhodamine 101 and LiF are used.
The architecture of the PSCs with double interlayers is
shown in Fig. 1(b). A thin layer of PEDOT:PSS was coated on a
pre-cleaned ITO glass. The photoactive layer was deposited by
spin coating a solution of 0.14 M PbCl2, 1.26 M PbI2 and 1.3 M
methylammonium iodide (MAI) in a cosolvent of dimethyl
sulfoxide (DMSO) and -butyrolactone (GBL) (vol. ratio = 3 : 7)
in a glove box filled with highly pure nitrogen. The solution
was spin coated at 1000 rpm for 20 s then at 5500 rpm for
60 s. At 40 s, the wet spinning film was quenched by dropping
160 l of anhydrous toluene. After spin coating, the film was
annealed at 100 C for 20 min. The thickness of the
CH3NH3PbI3xCl3 layer was ca. 260 nm. The incorporation of a
small amount of chlorine in the perovskite layer can improve
the free charge carrier lifetime and diusion length.30 On top
of the perovskite layer, a ca. 50 nm-thick PCBM was deposited.
Subsequently rhodamine 101 was deposited by spin coating
0.05 wt% rhodamine 101 solution in isopropanol (IPA) at
2000 rpm. 1 nm-thick LiF was then thermally evaporated. The
devices were completed by the thermal deposition of the Ag
electrode with a thickness of 100 nm. The rhodamine 101 and
LiF layers are the double interlayers between the electrontransport PCBM layer and the Ag electrode. The details of PSC
fabrication process are provided in ESI. Fig. S1 presents the
cross-sectional SEM image of a real device without the double
interlayers and the top Ag electrode.
Forming a smooth and uniform perovskite layer is critical
to the performance of the planar PSCs. In this study, we have
adopted a modified two-step method reported by Jeon et al. to
form the perovskite layer.6 In such a method, the introduction
of toluene during rapid spinning reduces the solubility of
CH3NH3PbI3xClx in the cosolvent of DMSO and GBL, thereby
promoting fast nucleation and growth of the crystals on the
film.31 In order to limit the rapid growth of perovskite crystals
for producing compact and uniform films, slightly more Pb2+
ions are introduced (Pb2+ : MAI = 1.4 M : 1.3 M), and a more
concentrated solution is used (1.4 M instead of 0.8 M). The
slight excess of PbI2 is used to passivate the perovskite grain
boundaries and relevant interfaces, which can suppress the
charge carrier recombination.32 Fig. 2(a) shows the X-ray
diraction (XRD) patterns of PbI2, MAI and CH3NH3PbI3xClx
perovskite films. XRD patterns of MAI are absent in that of
the perovskite film, suggesting that all the MAI has been consumed to produce perovskite. Because of the excess PbI2 in the
precursor solution, there is still a trace amount of PbI2 in
the perovskite film, evidenced by the small peak at 12.8

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Fig. 2 (a) XRD patterns of PbI2, CH3NH3I and CH3NH3PbI3xClx. (b)

UV-Vis absorption spectra of a CH3NH3PbI3xClx perovskite lm and
that coated with a 50 nm-thick PCBM layer or a PCBM + 1 nm-thick
rhodamine 101 layer. Inset shows a digital picture of the perovskite lm
deposited on PEDOT:PSS coated ITO glass.

that belongs to the PbI2 crystals. The XRD results are fully consistent with the reports of other labs.32,33
The perovskite layer is semi-transparent and dark brown in
colour (as shown in inset of Fig. 2(b)). Fig. 2(b) displays the
UV-Vis spectra of the perovskite layer and also that covered
with PCBM or PCBM/rhodamine 101. The absorption onset of
the perovskite layer is at ca. 780 nm, corresponding to an
optical bandgap of 1.59 eV. Subsequent coating of PCBM and
rhodamine 101 hardly aects the light absorption of the perovskite layer. The absorption profile of perovskite films with
PCBM or PCBM/rhodamine 101 layers remains the same as
that of the perovskite layer. In fact, the PCBM layer can
improve the stability of the perovskite. The perovskite film
without the PCBM layer turns grey and opaque after one day in
air, while the one with PCBM remains intact (see Fig. S2). Presumably, the thin PCBM layer on top of the perovskite layer
can potentially slow down the diusion of water and oxygen
from air into the perovskite.
The morphology and surface textures of the perovskite layer
without and with the PCBM or PCBM/rhodamine 101 layers

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Fig. 3 (a) SEM image and (b) AFM image of a perovskite lm. AFM
images of (c) the perovskite/PCBM (50 nm) lm and (d) the perovskite/
PCBM (50 nm)/rhodamine 101 (1 nm) lm. The height scale bar is
100 nm for (b) and 30 nm for (c) and (d). Root-mean-square roughness
(Rrms) values are indicated on the AFM images.

are investigated by scanning electron microscopy (SEM) and

atomic force microscopy (AFM) in tapping mode. SEM image
of the perovskite layer (Fig. 3(a)) shows that the perovskite crystalline grains are in sub-micrometer sizes and they form a
uniform dense film. The perovskite layer completely covers the
PEDOT:PSS layer. The structures showing a bright contrast
located at the grain boundaries are likely to be the less conductive PbI2 species. This observation is consistent with that
reported by Chen et al.32 AFM images show that the surface of
the perovskite layer becomes smoother and void-free after
coating with PCBM or PCBM/rhodamine 101 (Fig. 3(b)(d)).
The root-mean-square roughness (Rrms) decreases dramatically
from 16.1 nm for the perovskite layer to 3.2 nm after the deposition of the PCBM layer, and finally down to 2.2 nm after the
deposition of the rhodamine 101 layer.
The PSCs were encapsulated with epoxy and glass sheets.
They were then tested under AM1.5G illumination (100 mW
cm2) in air. The current density ( J)voltage (V) curves of the
PSCs with dierent cathode configurations are shown in Fig. 4(a).
Their related photovoltaic parameters are summarized in
Table 1. Without any cathode interlayer, the JV curve has an
S-shape in the voltage range from 0.1 to 1.1 V. This implies a
large internal resistance in the device of glass/ITO/PEDOT:PSS/
CH3NH3PbI3xClx/PCBM/Ag.34,35 The maximum PCE is 9.2%
and the average PCE of 6 devices from two batches is 8.5%.
Insertion of a 1 nm-thick LiF layer between the PCBM layer
and the Ag electrode simultaneously improves the open-circuit
voltage (Voc) and the fill factor (FF) so as to increase the PCE.
The maximum and average PCEs are 11.0% and 10.5%,
respectively. Rhodamine 101 can help the electron collection
more eciently than LiF. When a rhodamine 101 layer with a

898 | Nanoscale, 2015, 7, 896900

Fig. 4 (a) JV characteristics of perovskite solar cells with dierent

cathode congurations tested under AM1.5G illumination (100 mW
cm2); (b) IPCE curves of the respective perovskite solar cells.

thickness of ca. 1 nm is used as the interlayer between PCBM

and Ag, the FF dramatically increases from 0.53 to 0.74 while
Jsc and Voc stay almost constant. The maximum PCE of the
PSCs reaches 12.1%. The eciency increase by the rhodamine
101 layer is not related to the solvent used for rhodamine 101
processing. Control PSCs fabricated by spin coating pure IPA
without rhodamine 101 on the PCBM layer exhibit photovoltaic
performance similar to that of PSC without any electron-collection interlayer.
To understand the mechanism for the improvement in the
photovoltaic eciency of PSCs by the LiF or rhodamine 101
interlayer, the JV curves of devices were recorded in the dark
(Fig. S3). Both LiF and rhodamine 101 could simultaneously
improve the current injection under the forward bias and suppress the leakage current under reverse bias. Rhodamine 101
produced an even better diode-behaviour than LiF. To quantify
these changes, series resistance (Rs) and shunt resistance (Rsh)
were extracted from the dark currents at 2 V and 0 V, respectively (Table 1). The Rs value drops from 7.4 cm2 for glass/
ITO/PEDOT:PSS/CH3NH3PbI3xClx/PCBM/Ag to 5.1 cm2
and 3.5 cm2 for glass/ITO/PEDOT:PSS/CH3NH3PbI3xClx/
PCBM/LiF/Ag and glass/ITO/PEDOT:PSS/CH3NH3PbI3xClx/
PCBM/rhodamine 101/Ag, respectively. In addition, the Rsh
value increases close to 40 and 20 times after the insertion of
LiF and rhodamine 101, respectively.

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Table 1 Photovoltaic performances of perovskite solar cells having a cell architecture of ITO/PEDOT:PSS/CH3NH3PbI3xClx/cathode tested under
AM1.5G illumination (100 mW cm2)

Cathode configuration

Jsc
(mA cm2)

Voc (V)

FF

PCE [best
(average)a] (%)

Rs
( cm2)

Rsh
(k cm2)

Jsc from IPCE

(mA cm2)

Ag
LiF/Ag
Rhodamine 101/Ag
IPA washed
Rhodamine 101/LiF/Ag

17.71 0.47
17.11 0.23
17.86 0.42
17.49 0.51
17.72 0.37

0.91 0.01
1.02 0.01
0.90 0.01
0.91 0.01
1.01 0.01

0.53 0.02
0.60 0.02
0.74 0.02
0.53 0.03
0.73 0.02

9.2 (8.5)
11.0 (10.5)
12.1 (11.9)
9.1 (8.4)
13.2 (13.1)

7.4
5.1
3.5
5.2
5.1

44
1621
787
3534
134

18.02
17.90
18.68
17.65
17.97

The average results are derived from 6 perovskite solar cells made from two separate batches.

Since LiF mainly enhanced Voc of PSCs while rhodamine

101 enhanced FF, double interlayers of LiF and rhodamine 101
were used in PSCs. Both Voc and FF of the devices (glass/ITO/
PEDOT:PSS/CH3NH3PbI3xClx/PCBM/rhodamine 101/LiF/Ag)
are higher than those of the devices without any electroncollection interlayer (glass/ITO/PEDOT:PSS/CH3NH3PbI3xClx/
PCBM/Ag). Voc increases from 0.91 to 1.01 V, and FF increases
from 0.53 to 0.73. The double interlayers hardly aect Jsc.
Thus, the best PCE becomes 13.2%, which is higher than
those of the control devices without any electron-collection
interlayer or only one interlayer of either LiF or rhodamine
101. The Voc and FF values are comparable or even higher than
those of PSCs with a similar structure as reported in the
literature.2025
Finally to verify the Jsc values obtained from JV curves, the
incident photon-to-current eciency (IPCE) was acquired for
the best PSCs with dierent cathode configurations (Fig. 4(b)).
All the cells showed a broad absorption range from 300 nm to
800 nm. The IPCE values for all the cells are 7080% in the
wavelength range from 450 to 750 nm. The calculated Jsc
values by integrating the product of IPCE and solar irradiance
at each wavelength are summarized in Table 1. These values
were consistent with measured Jsc values derived from JV curves.

Conclusions
In summary, LiF and a zwitterionic small molecule, i.e. rhodamine 101, were chosen to improve the cathode interface
between the PCBM hole blocking layer and the Ag black electrode for planar perovskite solar cells. A single interlayer of LiF
(or rhodamine 101) can improve the PCE of PSCs by enhancing
Voc (or FF). The PCE is 9.2% for the PSC without any electroncollection layer. It increases to 11.0% and 12.1% after the
introducing a single interlayer of LiF and rhodamine 101,
respectively. Double interlayers of rhodamine 101 and LiF can
simultaneously increase Voc and FF so as to achieve higher
PCE. The best PCE reaches 13.2% for the PSCs with rhodamine
101/LiF double interlayers.

Acknowledgements
This work was supported by a research grant from the Ministry
of Education in Singapore (R-284-000-113-112).

This journal is The Royal Society of Chemistry 2015

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