Accepted Manuscript

Title: CH3 NH3 PbI3 Perovskite Sensitized Solar Cells Using a

D-A Copolymer as Hole Transport Material
Author: P. Nagarjuna K. Narayanaswamy T. Swetha G.
Hanumantha Rao Surya Prakash Singh G.D. Sharma
PII:
DOI:
Reference:

S0013-4686(14)02180-X
http://dx.doi.org/doi:10.1016/j.electacta.2014.11.003
EA 23675

To appear in:

Electrochimica Acta

Received date:
Revised date:
Accepted date:

12-8-2014
30-10-2014
1-11-2014

Please cite this article as: P.Nagarjuna, K.Narayanaswamy, T.Swetha, G.Hanumantha

Rao, Surya Prakash Singh, G.D.Sharma, CH3NH3PbI3 Perovskite Sensitized Solar
Cells Using a D-A Copolymer as Hole Transport Material, Electrochimica Acta
http://dx.doi.org/10.1016/j.electacta.2014.11.003
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CH3NH3PbI3 Perovskite Sensitized Solar Cells Using a D-A Copolymer as Hole

Transport Material
P. Nagarjuna1, K. Narayanaswamy1, T. Swetha1, G. Hanumantha Rao1, Surya Prakash
Singh1* and G. D. Sharma2*
1

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,

Uppal road, Tarnaka, Hyderabad-500007, India
2

R & D Center for Engineering and Science, JEC group of Colleges, Jaipur Engineering
College, Kukas, Jaipur 303101, India
Graphical abstract
fx1

conjugated

D-A

copolymer

(P)

having

PT

Abstract
benzodithiophene

donor

and

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benzo[1,2,5]thiadiazole acceptor was employed as a p-type hole transporting material in solid

SC

state organicinorganic hybrid solar cells and compared with the P3HT hole transporting
material. In these device we have used organo-lead halide (CH3NH3PbI3) synthesized by us,

as light harvester. The power conversion efficiency (PCE) of 6.64 % is achieved for the solar

cell with P which is higher than that for P3HT (4.24 %). The increase in PCE is mainly due to

the enhancement in FF and Voc and attributed to higher mobility of hole for conjugated

copolymer than P3HT.

Key words: Inorganic-organic hybrid solar cells, perovskite, donor--acceptor, hole transport
material, power conversion efficiency.

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* Corresponding authors

spsingh@iict.res.in (Surya Prakash Singh)

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Tel: +91-40-27191710; Fax: +91-40-27160921

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gdsharma273@gmail.com (G. D. Sharma)

1. Introduction
Dye sensitized solar cells received considerable attention since the first report on 1991 by

Grtzel and his coworkers, due to the excellent power conversion efficiency (PCE) of about
7% at a relatively low cost of fabrication1 and are alternative to the conventional silicon
based solar cells. A typical DSSC uses a monolayer of light absorbing sensitizer anchored on
nanocrystalline TiO2 to enhance light harvesting in a mesoporous environment in which

charge separation also occurs at this surface. Lot of research has been carried out to enhance
the PCE of these devices. As a result, PCE of 12.3 % has been reported in 2011, by Grtzel
research group for DSSCs based on an ortho-substituted porphyrin sensitizer, YD2-oC8,
cosensitized with organic dye (Y123) with a cobalt electrolyte2 which opened a new research
area on porphyrin sensitized DSSCs.3 However, the absorption spectrum of this porphyrin
dye covers only the visible spectral region and lack of light harvesting ability beyond 700 nm
limits the further enhancement in PCE for the DSSCs based on porphyrin dyes. Moreover, the
long term stability of these devices might be an issue for future commercialization due to the
use of volatile electrolytes. Various inorganic light absorbers with light harvesting capability

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that extends into the near infrared region were hence sought to replace these organic dyes.
Recent studies have reported that organometal halide perovskite mesoscopic solar

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cells with promising PCEs due to their excellent light harvesting and electron transporting
properties and are perfectly suitable for use as prospective photovoltaic materials. In 2009,

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Miyasaka et al. reported the first perovskite (CH3NH3PbBr3) sensitized TiO2 solar cell using
liquid electrolytes based on iodide and bromide and achieved a PCE of 3.1 % under one sun

illumination and 3.8 % when CH3NH3PbBr3 was replaced by CH3NH3PbI3.4 Later on Park et

al.5 in 2011, reported improved PCE of 6.5 % for modified TiO2 solar cells sensitized with

CH3NH3PbI3 perovskite and an electrolyte based on iodide. They have used Pb(NO3) for

modify the surface of mesoporous TiO2 film before coating of perovskite film and acts as
blocking layer in the solar cells. However, it was observed that the performance of devices

based on perovskite materials and liquid electrolyte decreased by 80 % in only few hours due

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to the instability of the perovskite material in the presence of liquid electrolyte due to the
dissolution of perovskite. Hence it is essential to prepare perovskite based solar cells with a

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solvent free hole transport material (HTM) and called as solid state organic-inorganic hybrid
solar cells. Park and coworkers6 reported sub-micrometer thin film solid state solar cells
7

Snaith and co-

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attaining a PCE of 9.7 % with a CH3NH3PbI3 in mesoporous TiO2 film.

workers reported a similar perovskite, CH3NH3PbI3Cl that served as a light absorber for

mesoscopic thin film solid state solar cells to attain a PCE of 10.9%, for which the
mesoporous Al2O3 film served as scaffold to replace the n-type TiO2 electron transporting
layer. Recently, same group reported a significant enhanced PCE of 12.3% 8 for perovskite
CH3NH3PbI3-xClx solar cells, with the same device structure based on Al2O3. Soak et al.
reported almost same PCE for solar cell based on another perovskite CH3NH3Pb(I1-xBrx)3,
with the mesoporous TiO2 photoanode.9 Recently, in 2013, Grtzel and co-workers, reported
perovskite CH3NH3PbI3 sensitized TiO2 solar cells with a PCE approaching to 15 % which

set a new record for all solid state hybrid mesoscopic solar cells.10 Therefore, this impressive
PCE opened new channel for the development of third generation solar cells based on
perovskite and HTM with the advantages of very high PCE, low cost, ease of processing and
considerable durability11 and efficiency approaching 20% is realistically possible from a
solid-state mesoscopic solar cell based on CH3NH3PbX3 (X = Cl, Br, or I).12 In all above
perovskite solar cells, a HTM [2,2,7,7-tetrakis-(N,N-di-pmethoxyphenylamine) 9,9-spirobifluorene] (spiro-OMeTAD) has been employed. However, conductivity of spiro-OMeTAD
is low (~10-5 S/cm). Moreover, the spirobifluorene core in spiro-OMeTAD molecule is
relative expensive due to extensive synthetic processes for preparation. So it would be

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important to develop a cheaper alternative of spiro-OMeTAD for commercial application of

hybrid perovskite solar cells.

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Alternative HTM materials with excellent electrical properties may be used in place
of spiro-OMeTAD. Soluble donor--acceptor (D--A) can be the alternative choice as HTM.

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Conjugated polymers have been widely used in the field of polymer solar cells because of
their easy processability, low cost and mechanical flexibility.13 The solar cells using the

combination of perovskite with mesoporous TiO2 and P3HT as hole transport material, PCEs

of 3.8 %, 4.5 %14 and 6.7 %15 have been reported and recently a PCE of 10.8 % have been

achieved by Coning et al. for CH3NH3PbI2Cl perovskite.16

To obtain high photovoltaic performance, it is importance that the HTM should show
a good hole mobility and compatible highest occupied molecular orbital (HOMO) energy

level to the semiconductor light absorber. Recently, Qiu, have used a p-type low band gap

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conjugated D-A copolymer PCBTDPP as HTM and achieve an outstanding open circuit
voltage of about 1.15 V for CH3NH3PbBr3 sensitized hybrid solar cells and CH3NH3PbI3

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sensitized hybrid solar cell showed a PCE of 5.55% along with good stability.17 Heo et al
have reported a ~12 %18 PCE in an organic-inorganic hybrid solar cell using a poly

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(triarylamine) (PTAA) HTM with an average PCE of 9.7% 19 The D-A conjugated polymer P
(chemical structure shown in Figure 1) have the deeper HOMO level than P3HT and posses

good stability than P3HT. Recently, Sharma et al have used this copolymer as donor material
for polymer solar cell along with PCBM and achieved a PCE of 3.45-5.30%.20 These
demonstrations indicate that the P can be used as HTM for hybrid solar cells.
In the present communication, we have used D-A conjugated copolymer P as HTM to
investigate the solid state hybrid solar cells consisting of CH3NH3PbI3 as the light harvester
and mesoporous TiO2 as photoanode. We have also fabricated the solar cells using P3HT as

HTM for comparison. The inorganic-organic hybrid solar cell with P as hole transport
material (PCE=6.64 %), showed higher PCE than that for P3HT (PCE=4.24 %) and attributed
to the higher hole mobility of P as compared to P3HT. The enhancement in Voc and FF for
cell with P has been related to the deeper HOMO energy level of P and efficient hole
transport, respectively.
2.

Experimental details

Perovskite was synthesized following the reported procedure.6 The P3HT was purchased
from Aldrich and copolymer was synthesized as reported earlier.20
2.1 Device fabrication and characterization

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A 40 nm thick dense blocking layer of TiO2 was deposited onto the pre-cleaned FTO
substrate by spraying pyrolysis deposition carried out using a 20 mM titanium diisopropoxide

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bis(acetylacetone) solution (Aldrich) at 450 C to prevent direct contact between FTO and
HTM. The mesoporous TiO2 films were coated from a TiO2 paste (dye Sol 18NT-T paste

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diluted in anhydrous ethanol) by doctor blade technique. The films were dried at 80 C for 1
min and then annealed at 450 C for 30 min. The films were then treated in 40 mM of TiCl4

aqueous solution at 60 C for 1 hr and heat treatment at 450 C for 30 min to improve the

interfacial contact with nanocrystalline TiO2. The perovskite CH3NH3PbI3 solution was

prepared as follow. The synthesized CH3NH3I powder was mixed with PbI2 at a 1:1 mol

ratio in dimethylformamide (DMF) and stirred over night at 60 C, followed by filtering

using a Whattman (0.45 m) filter paper. The prepared solution of perovskite was dripped on

the top of TiO2 film and then spin cast at 2500 rpm for one minute. After that the perovskite

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sensitized TiO2 film was placed on a top of hot plate at 100 C for 45 min to form crystalline
CH3NH3PbI3. The heat treatment is essential for a complete conversion of precursor to final

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organo lead halide. The heated CH3NH3PbI3 film exhibits better optical absorption and higher
crystallinity.21 We have used P3HT (commercially available and used without any further

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purification)

and

copolymer

P.

The

polymer

HTMs

were

spin

coated

on

CH3NH3PbI3/TiO2/bl-TiO2 /FTO substrate at 2500 rpm for 30s using HTMs solution in

chlorobenzene and then dried for 1 hr. Finally a gold (Au) cathode electrode was deposited
by thermal evaporation using a shadow mask to fix the active area of device around 0.20 cm2.
The current-voltage (J-V) characteristics under illumination as well as in dark, of the
devices were recorded using a Keithley source meter (model 2400). A xenon lamp coupled
with AM 1.5 optical filter (100 mW/cm2) was used as light source for illumination. The
incident photon to current conversion efficiency (IPCE) of the devices was measured using a

monochromator and xenon lamp as light source and resulting photocurrent was measured
with source meter under short circuit condition.
3.

Results and discussion

The optical UV-visible absorption spectra of perovskite CH3NH3PbI3 thin film is

shown in Fig. 2. It can be seen from this figure that the thin film of synthesized perovskite
(annealed at 100 C) absorbs a wide range of light from visible to the near infrared with an
absorption onset at 790 nm, indicating the formation of CH3NH3PbI3 film on the substrate22.
The CH3NH3PbI3 film exhibits an absorption peak around 370 nm and a shoulder band at 484
nm. The optical band gap estimated from the absorption onset wavelength is 1.57 eV is in

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agreement with the value reported in literature. We had also characterized the thin film of
CH3NH3PbI3 by X-ray diffraction and shown in Fig. 3. The appearance of strong peaks at

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2=13.98, 28.32 and 31.74 corresponds to the (110), (220) and (310) planes, indicates the
formation of the tetragonal perovskite structure.23

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We have used a low bandgap D-A copolymer with 4,8-bis-(5-bromothiophene-2-yl)benzo[1,2,5] thiadiazole as donor unit having HOMO and LUMO energy level of -5.24 eV

and -3.48 eV, respectively. This copolymer showed a strong absorption band in 590-800 nm

(Fig.2). The energy levels of copolymer P are well matched with the CH3NH3PbI3

(conduction band and valance band edge were about -3.92 and -5.96 eV, respectively) for

efficient charge separation. The valance band of this perovskite is lower than the HOMO of
conjugated polymer P. Additionally, conduction band of CH3NH3PbI3 is sufficient higher

than that of the TiO2 and lower than LUMO of P. Hence, this copolymer P may promote

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charge transport in the hybrid solar cells, when used as HTM.

Fig. 4 shows the current-voltage (J-V) characteristics of the devices with and without

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P3HT and P as HTM, under illumination AM1.5 (100 mW/cm2) and the photovoltaic
parameters are summarized in table 1. The cell with P as HTM, shows a PCE of 6.64 % with

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Jsc = 11.98 mA/cm2, Voc = 0.84 V and FF = 0.66, where as P3HT as HTM based cell
exhibited a PCE of 4.24% with Jsc = 11.83 mA/cm2, Voc= 0.64 V and FF = 0.56. As can be

seen from figure and table 1, the cell fabricated without HTM also exhibit relatively good
photovoltaic response (Jsc =9.22 mA/cm2, Voc=0.62 V and FF= 0.48 and PCE = 2.74 %),
though it is inferior to the cells with HTM due to decrease in the Jsc, Voc and FF. This
confirms that photogeneration of charge carrier occurs at the TiO2/CH3NH3PbI3
heterojunction24 and the device acts as p-n junction solar cell. In this device, CH3NH3PbI3
acts simultaneously the roles of both light harvester and hoe transporter. Moreover, the

interface between perovskite/ HTM is beneficial to the hole transfer and leading to the higher
value of Jsc and FF.
As can be seen from the absorption spectra of P3HT and P that these HTM exhibit
absorption peak at 520 nm and 595 nm respectively. The IPCE spectra of the devices based
with P3HT and P HTM and without HTM are shown in Fig. 5. The spectral overlap between
the HTM and perovskite often reduces the light harvesting efficiency of the perovskite and
thus loss in the photocurrent of the device. The IPCE spectra of the devices closely matched
with the absorption spectra of the perovskite, indicating that in spite of the absorption peak of
P3HT and P are about 520 nm and 595 nm, respectively, the polymers does not contribute to

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the photocurrent. Moreover, the similar shape of IPCE spectra for both devices attributed that
light absorption by the polymer is negligible and the role of these polymers is limited to the

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charge transporting layer. The cell with P yields relatively higher IPCE values at most of the
wavelengths than the cell with P3HT. This finding is consistent with the slightly higher value

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of Jsc for former device, obtained from J-V characteristics, under illumination.
The value of Jsc for device based on P is slightly higher than that for P3HT counter

part, whereas Voc and FF are significantly higher the device based on P. It is reported that the

Voc of a hybrid solar cell is closely related to the difference between the quasi Fermi level of

electrons in TiO2 (n-type semiconductor), under illumination and HOMO level of the p-type

HTM. The conjugated copolymer P has a HOMO energy level of -5.24 eV is deeper than that
of P3HT (-5.1 eV), resulting higher value of Voc for the cell based on P as HTM. The

difference in the HOMO level of P and P3HT is only about 0.14 eV, but the difference in the

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Voc is about 0.20 V. Therefore, the Voc may be attributed to the charge recombination
kinetics. The J-V characteristics of the devices in dark (Fig. 6) can give the information of

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charge recombination kinetics in the device. As shown in Figure the device with P has
relatively lower dark current and an upper shift in onset, compared to P3HT. This implies that

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P has a superior electron blocking ability than P3HT. Since the dark current is the measure of
the recombination current. The small dark current means reduction in the back electron

recombination. This reduction pushes the quasi Fermi level of TiO2 upwards (more negative),
thereby enlarging the difference between the HOMO of P and quasi Fermi level of TiO2,
resulting contribution to the enhancement in Voc. Moreover, the high value of Voc for P as
compared to P3HT is in agreement with the relative difference in the HOMO levels of P and
P3HT because the energy level offset between the HOMO level of donor (HTM) and the
LUMO level of acceptor (perovskite) modulates the magnitude of Voc.

It is worth noting that the Jsc of the P based cell is slightly higher than that for P3HT
despite of small energetic driving force of regeneration of oxidized perovskite for former
device as compared P3HT. Since a driving force of 0.30 mV is sufficient for the regeneration
of oxidized perovskite, the off set between the HOMO level of P and valance band edge of
perovskite is sufficient for regeneration but lower than that for device based on P3HT. As the
back charge recombination for device based on P is suppressed, we explain the slight increase
in Jsc by assuming that slow regeneration rate (transfer of electron from P to perovskite) was
compensated by the fast charge transport in P HTM medium as compared to P3HT. The
difference in the FF can be understand with the assumptions described by Burschka et al.,
who demonstrated that the conductivity (charge carrier mobility) of an organic semiconductor

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is important for achieving a high photovoltaic performance of the device.25

We have

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measured the charge carrier mobility by fitting J-V characteristics in dark with space charge
current limited model. The hole mobility of P is about 6.68 x10-4 cm2/Vs which is higher than

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that for P3HT (2.45 x10-4 cm2/Vs). Therefore, the P exhibited a higher conductivity than
P3HT indicates that conjugated polymer P facilities hole transport more efficiently that

P3HT.26 The FF is related to the series resistance (Rs) and shunt resistance (Rsh). In order to

obtain a high FF solar cell should exhibits a low Rs and high Rsh. The main difference in the

devices investigated here is the HTM. This means that the FF value can be partly ascribed to

the increased hole transporting and electron blocking ability of HTM, which could suppress
the possibility for the photogenerated charges to recombine before they reach to the

collecting electrode. Moreover, the space charge effect in reduced in the TiO2/perovskite/P

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junction as compared to the TiO2/perovskite/P3HT junction due to the small difference in the
mobility between electron and hole. It can be also seen from the J-V characteristics under

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illumination, the series resistance (reciprocal of slope of J-V characteristics at Voc) is lower
for the device with P as compared to P3HT counterpart also consistent with the fact that the

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hole mobility for P is higher than that for P3HT. The higher value of FF for solar cell with P
compared to P3HT counterpart may be ascribed to the reduced series resistance and fast

charge transport. Moreover, the space charge effect in reduced in the TiO2/perovskite/P
junction as compared to the TiO2/perovskite/P3HT junction due to the small difference in the
mobility between electron and hole, resulting balanced charge transport6,27 leading to an
increase in the FF and PCE.
4.

Conclusion
In summary, we have fabricated a solid state organic-inorganic hybrid solar cells

based on a CH3NH3PbI3 perovskite as light harvester and P3HT and D-A conjugated

copolymer P as hole transporting materials. The solar cell based on P showed a considerable
higher performance than that for P3HT. The Jsc of the solar cell based on P is slightly higher
than that for P3HT, but improvement in PCE was attributed to the mainly due to the
enhanced Voc and FF.
Acknowledgment
We are thankful to Prof. M.L. Keshtov, Institute of Organoelement Compounds of the
Russian Academy of Sciences, Vavilova, Moscow, for providing the copolymer. We are also
thankful to Dr. S. Biswas, Department of physics, LNMIIT, Jaipur for providing the facilities
for device fabrication and their characterization. PN thanks to CSIR for providing senior

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research fellowship. SPS thanks to XII FY CSIR-INTELCOAT (CSC0114) for financial

support.

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Nazeeruddin, M. K.; Grtzel, M. Tris(2-(1H-pyrazol-1-yl)Pyridine)Cobalt(III) as ptype Dopant for Organic Semiconductors and Its Application in Highly Efficient SolidState Dye-Sensitized Solar Cells. J. Am. Chem. Soc. 2011, 133, 18042-18045.

TE

26 (a) Snaith, H. J.; Grtzel, M. Enhanced Charge Mobility in a Molecular Hole

Transporter via Addition of Redox Inactive Ionic Dopant: Implication to DyeSensitized Solar Cells. Appl. Phys. Lett. 2006, 89, 262114, (b) Scholin, R.; Karlsson,
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Shifts in Spiro-OMeTAD Molecular Thin Films When Adding Li-TFSI. J. Phys.
Chem. C 2012, 116, 2630026305.

CC

EP

27 L. J. A. Koster, V. D. Mihailetchi, H. Xie and P. W. M. Blom, Appl. Phys. Lett., 2005,

87, 203502

Table 1 Photovoltaic performance of devices

Jsc (mA/cm2)

Voc (V)

FF

PCE

Without HTM

9.22

0.62

0.48

2.74

P3HT

11.83

0.64

0.56

4.24

11.98

0.84

0.66

6.64

PT

CC

EP

TE

SC

RI

Fig. 1 Chemical structure of D--A conjugated copolymer P and P3HT

Fig. 2 Normalized absorption spectra of CH3NH3PbI3, P and P3HT

RI

PT
CC

EP

TE

SC

Fig. 3 XRD pattern of CH3NH3PbI3 film

Fig. 4 Current voltage characteristics of the device using P, P3HT HTM and without HTM,
under illumination (100 mW/cm2)

PT
RI
SC

CC

EP

TE

Fig. 5 IPCE spectra of solar cells with P and P3HT HTMs and without HTM

Fig. 6 Current voltage characteristics of the device in dark using P and P3HT as HTM

TOC

CC

EP

TE

SC

RI

PT

CH3NH3PbI3 Perovskite Sensitized Solar Cells Using a D-A Copolymer as Hole

Transport Material
P. Nagarjuna, K. Narayanaswamy, T. Swetha, G. Hanumantha Rao, Surya Prakash Singh and
G. D. Sharma