Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Hybrid solar cell based on blending of organic and inorganic materials—An

overview
J. Chandrasekaran a,*, D. Nithyaprakash a, K.B. Ajjan a, S. Maruthamuthu a, D. Manoharan a, S. Kumar b
a
Department of Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore 641 020, Tamilnadu, India
b
School of Environment, Resources and Development, Asian Institute of Technology, PO Box 4, Klong Luang, Pathumthani 12120, Thailand

A R T I C L E I N F O A B S T R A C T

Article history: In recent years, increasing efficiency in organic solar cells is due to the bulk heterojunction concept.
Received 2 June 2010 Hybrid solar cell (HSC) based bulk heterojunction is flourishing in the field of solar cell. This device is the
Accepted 9 September 2010 combination of inorganic and organic materials. The efficacy of the power conversion efficiency has
reached above 5% by following this combination method. This review provides general introduction,
Keywords: principle, working and characterization in the HSC involving the blend of organic/inorganic material as
Bulk heterojunction active layer. Different material combinations of the active layer and their performance are tabulated for
Organic/inorganic hybrid
better understanding of the HSC. This review ensures total compliance by discussing the fabrication
Nanomaterials
technologies in terms of the HSC concept.
Active layer
Power conversion efficiency ß 2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1228
2. Principle and working of hybrid solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1229
3. Characterization of hybrid solar cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1229
4. Review of hybrid solar cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
5. Results and discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236

1. Introduction electrode [1]. About 50 years later, Charles Fritts constructed the
first true solar cells using junctions formed by coating the
Solar cells are designed to convert available light into electrical semiconductor selenium with an ultra thin, nearly transparent
energy. They do this without the use of either chemical reactions or layer of gold. Fritts’s devices were very inefficient, transforming
moving parts. Solar cells are usually made from silicon, the same less than 1% of the absorbed light into electrical energy [2,3]. By
material used for transistors and integrated circuits. The silicon is 1927 the transferring capacity of another metal-semiconductor
treated or ‘‘doped’’ in order to create charge carriers, so that when junction solar cell, made of copper and the semiconductor copper
light strikes it electrons are released, leading to generation of oxide, had been demonstrated. Towards 1930 both the selenium
electric current. The work of the French physicist Antoine – Cesar cell and the copper oxide cell were being employed in light-
Becquerel in 1839 laid the founding stone for the development of sensitive devices, such as photometers for the use in photography.
solar cells. Becquerel discovered the photovoltaic effect while These early solar cells, however, still had energy-conversion
experimenting with a solid electrode in an electrolyte solution. He efficiencies of less than 1%. This impasse was finally overcome with
observed the development of voltage when light fell upon the the development of the silicon solar cell by Russell Ohl in 1941. In
1954, American researchers, G.L. Pearson, Daryl Chapin, and Calvin
Fuller, demonstrated a silicon solar cell having 6% energy
* Corresponding author. Tel.: +91 422 2692461; fax: +91 422 2693812. conversion efficiency when used in direct sunlight [4,5]. By the
E-mail address: [email protected] (J. Chandrasekaran). late 1980’s silicon cells, as well as those made of gallium arsenide,

1364-0321/$ – see front matter ß 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2010.09.017
 [(Fig._1)TD$IG]
J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238 1229

with efficiencies of more than 20% had been fabricated [6,7]. In

1989 the concentrator solar cell, a type of device in which sunlight
is concentrated onto the cell surface by means of lenses achieved
an efficiency of 37% owing to the increased intensity of the
collected energy.
A broad range of solar cell technologies are currently being
developed, including dye-sensitized, nanocrystalline photoelec-
tron chemical solar cells, polymer/fullerene bulk heterojunctions,
small molecule thin films and organic/inorganic hybrid solar cells.
Hybrid solar cells are a mixture of nanostructures of both organic
and inorganic materials. Therefore, they combine the unique
properties of the inorganic semiconductor nanoparticle with those
of the organic/polymeric materials [8]. It consists of p-type
polymer semiconductor and an inorganic n-type material.
Currently, the highest efficiency for such hybrid device has been
obtained with CdSe nanoparticles and polythiophene.
In recent years, various solution processed bulk heterojunction
photovoltaic devices have been reported using p-type conjugated
polymers, in combination either with n-type polymers [9,10] or Fig. 1. Structure of hybrid solar cell.
with fullerenes [11–14]. Alternatively conjugated polymers have
been combined with n-type inorganic semiconductor nanoparti-
cles. These hybrid polymers/inorganic nanoparticle bulk hetero- blocker, but it also smoothens the ITO surface, seals the active layer
junction can take advantage of the beneficial properties of both from oxygen, and keeps the anode material from diffusing into the
types of materials such as solution processing of polymer active layer, which can lead to unwanted trap sites. Next, on the top
semiconductors and high electron mobility of inorganic semi- of the PEDOT:PSS, an active layer is deposited which holds the
conductors. So far, various hybrid polymer solar cells have been responsibility for light absorption, exciton generation/dissociation
reported, using CdSe nanodots, nanorods [15] and tetrapods and charge carrier diffusion. The active layer is made up of two
[16,17] and using of TiO2 [18], ZnO [19,20], PbS [21,22], PbSe materials namely donor and acceptor. Polymers are the common
[23,24], CuInS2 [25] and CuInSe2 [26]. In a related approach donors whereas nanoparticles act as common acceptors. Cathode,
nanostructured TiO2 has been filled with conjugated polymers typically made of Al, Ca, Ag and Au was coated on top of the active
[27–32], but highest efficiency was recorded in the random layer
mixtures of conjugated polymers and inorganic nanoparticles. In The I–V characterization of the hybrid solar cell device is shown
order to obtain hybrid polymer solar cells with high current and fill in Fig. 2. In the dark, I–V curve passes through the origin indicating
factor, both electron and hole mobilities must be optimized and the absence of potential and current. But when the device is
most importantly balanced. Improvement of the performance of exposed to light, the I–V curve shifts downwards.
these devices is often sought in improving electron transport
through inorganic component. In this paper, the researchers have 3. Characterization of hybrid solar cell
focused only on HSC where organic and inorganic materials
composites or blend are used, excluding tandem, dye and The following terms are often used to characterize solar cells,
copolymer based cells. some items are also shown in the I–V graph:

2. Principle and working of hybrid solar cells (i) Air mass: It is the ratio of the path length of the sun rays
through the atmosphere when the sun is at a given angle u to
The developments of HSC’s basic principle have been outlined. the zenith. An air mass distribution of 1.5, as specified in the
In HSC based on bulk heterojunction concept, the donor and standard condition, corresponds to the spectral power
acceptor are blended in single photovoltaic layer. The light induces distribution observed when the sun’s radiation is coming
electron transfer from the donor to the acceptor. The charge from an angle to over head of about 488.
separation occurs throughout the active layer where the donor and
[(Fig._2)TD$IG]
acceptor are in contact. Once charge separation has occurred, the
challenge to prevent the reverse process, recombination and
delivering of charge to different electrodes occur. In these cells,
transport of charge carriers to the electrodes and suppression of
recombination are possible only if the donor and acceptor phases
are completely ordered.
A complete hybrid solar cell is pictured in Fig. 1. The hybrid
device generally has a transparent anode through which light
enters. Conventional solar cells typically allow light to enter from
the anode side while the anode itself consists of a grid of
conductive material. The hybrid solar cells consist of at least four
distinct layers, excluding the substrate, which may be glass. On the
top of the substrate, the anode is laid. Indium tin oxide (ITO) is a
popular anodic material due to its transparency and glass substrate
coated with ITO is commercially available. A layer of the
conductive polymer mixture PEDOT:PSS may be applied between
anode and the active layer. The PEDOT:PSS layer serves in several
functions. It not only serves as a hole transporter and exciton Fig. 2. I–V characteristics of hybrid solar cell.
 1230
Table 1
Review of hybrid solar cell based on blending of organic and inorganic materials.

S. No. Author’s name Aim of the work Experimental details Author’s remarks

1 Elif Arici Characterizing HSC based on nanoparticles of CuInS2 The device structure used was: In BHJ device (d) PCE was high (0.07%) compared to
et al. (2003) inorganic matrices. (a) ITO/PEDOT:PSS/CIS/LiF/Al single layer device (c) (0.003%) [33].
(b) ITO/PEDOT:PSS/CIS/PCBM/LiF/Al
(c) ITO/CIS:PEDOT:PSS/LiF/Al
(d) ITO/CIS:PEDOT:PSS blend/PCBM/LiF/Al.
2 Waldo J.E Beek Fabricating HSC from ZnO nanoparticles and a The structure of the cell was glass plate/ITO/ A PCE of 1.6% (0.71 sun equivalent) and 1.4% (1.7 sun
et al. (2004) conjugated polymer. PEDOT:PSS/MDMO-PPV:nc-ZnO blend/Al layer. equivalent) was obtained for the blended hybrid
solar cell which illustrated the effectiveness of using
a combination of organic and inorganic materials for
photovoltaic applications [19].

J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

3 Elif Arici Investigating blends of polyhexylthiophene (P3HT) The cell structure was ITO/CISe:P3HT blend/Al. Films consisting of TOPO-capped CISe:P3HT in a
et al. (2004) with copper indium diselenide nanocrystals for Blends of CISe/P3HT have been prepared by varying weight ratio of 6:1 showed a significantly better
photovoltaic applications. the amount of the CISe in the films. photovoltaic response in comparison with a P3HT
single layer [34].
4 Jinsong Liu Fabricating HSC using polythiophene and ncs of The device structure of the cell was ITO/PEDOT/ The end functional P3HTenhanced the performance
et al. (2004) CdSe. P3HT:CdSe ncs/Al. of P3HT: CdSe SC by increasing the dispersion of CdSe
ncs without introducing insulating surfactants [35].
5 Waldo J.E. Beek Preparing HSC using zinc oxide precursor and The fabrication process was ITO coated plate/ The PCE of 1.1% was reached for the use of precursor
et al. (2005) conjugated polymer. PEDOT:PSS/MDMO-PPV and ZnO blend/Al. ZnO device, and for ZnO np:MDMO-PPV blend it was
Annealing and drying were carried out in a perfect 1.6%, but Voc was found to be increased for the cell
manner. with precursor ZnO device [36].
6 Lenneke H. Slooff Investigating the influence of relative humidity on The bilayer and BHJ device with structure of ITO/ The bilayer device showed PCE was 0.3%. In BHJ the
et al. (2005) the performance of polymer/TiO2 PV cells. TiO2/MDMO-PPV/PEDOT:PSS/Au and ITO/ RH during spin coating strongly influenced the TiO2
PEDOT:PSS/MDMO-PPV:TiO2 blend/LiF/Al was structure and the device performance. Generally BHJ
fabricated for comparison. gives higher efficiency than a bilayer. But in the case
of BHJ efficiency was low owing to a lack of
crystalline in the TiO2 [37].
7 P.Y. Stakhira Investigating the electrical and photovoltaic The active materials used were SnO2/PAN–InSe The experiment proved that the V–I characteristic
et al. (2005) property of PAN–InSe composites. composite/Au. Volt–ampere characteristics of the PAN/p-type InSe micro particle exhibited rectifying
structure were described by Shockly equation. junction behavior and the proposed structure
showed a nonlinear dependence of current with light
intensity [38].
8 Andrew A.R. Watt Fabricating polymer solar cell using PbS nanocrystal. The cell was with a structure of ITO glass/PEDOT:PSS/ PCE for white light and single wavelength was
et al. (2005) PbS:MEH-PPV composite/Al. observed to be 0.7% and 1.1% [39].
9 Yi-Jun Lin Investigating organic–inorganic hybrid materials P3HT was coated on the top of P3MeT/TiO2/ITO. Al The PCE of the photovoltaic solar cell was
et al. (2006) based on the P3MeT and TiO2. was used as top electrode by the evaporation 3.22  103%. The efficiency was low owing to poor
deposition of 60 nm thick. contact between polymer and TiO2 [40].
10 Serap Gunes Fabricating HSC using HgTe nc and nanoporous TiO2 ASOS device was fabricated following the structure HgTe ncs were found to be optically active both in OS
et al. (2006) electrodes. ITO/nanoporous TiO2/HgTe-AS/ncs HgTe-OS:P3HT/ and AS device. It also helps to reduce the interfacial
Au. Reference device AS was prepared in identical charge carrier recombination at nanoporous TiO2
manner but with only HgTe-AS nc on nanoporous interface. ASOS device performance was found to be
TiO2 and without HgTe-OS in P3HT. Reference OS higher than AS, OS and NO device [41].
was made with HgTe-OS ncs in polymer blend but
without HgTe-AS ncs on the nanoporous TiO2 surface
and Reference NO device was prepared without
nanocrystal.
11 Waldo J.E. Beek Investigating HSC from regioregular polythiophene The exact blends of ZnO and P3HT were made and PCE of 0.9% was obtained for this type of cell. Further
et al. (2006) and ZnO nanoparticles. spin casted on glass plate coated with ITO and improvement in the polymer chain or nanoparticles
PEDOT:PSS respectively followed by depositing Al by can enhance the performance [42].
means of thermal evaporation.
12 Sang-Hyun Choi Synthesis of size-controlled CdSe quantum dots and Size controlled CdSe Q-dots were synthesized by wet The hybrid solar cells made of CdSe Qdots-P3HT
et al. (2006) characterization of CdSe-conjugated polymer blends chemical method. PEDOT:PSS was spin coated on ITO polymer blends with the pyridine–chloroform
for hybrid solar cells. followed by CdSe Qdots-P3HTand CdSe Q dots-MEH- solvent mixture could achieve power conversion
PPV polymer solution containing 1–8 vol% of efficiencies of about 0.05%. It was also confirmed that
pyridine–chloroform. Al was used as working binary solvent mixtures play an important role in the
electrode. fabrication for hybrid solar cells [43].
13 Yi Zhou Investigating the effect of nc composites on the PV Tetra podal CdSexTe1x nc with different The optimal blend ratio of CdSe:MEH-PPV with 9:1
et al. (2006) properties of the SC. compositions was synthesized. ITO/PEDOT:PSS/ showed the highest PCE of 1.13% [44].
CdSe, CdSexTe1x and CdTe ncs were mixed with
MEH-PPV to form different structures/Al. The PCE
was recorded for different wt ratios of CdSe:MEH-
PPV.
14 Lili Han Fabricating hybrid solar cells based on zinc-blend ITO was spin coated with PEDOT:PSS. The CdSe ncs The photovoltaic cell obtained from the spherical
et al. (2006) CdSe ncs/MEH-PPV. were dissolved in a mixture of pyridine. Two master zinc-blend CdSe ncs with MEH-PPV reached an
solutions of MEH-PPV and CdSe ncs were mixed in energy conversion efficiency of over 0.85% [45].
desired ratios and the blended films with desired
thickness were spin coated on top of the dried
PEDOT:PSS. Finally, the Al cathode was thermally
deposited on top of the blended film.
15 L. Jan Anton Koster Studying the transport properties of blend MDMO- The material used for the fabrication was ITO/ The transport of charge carrier in MDMO-PPV and
et al. (2006) PPV/ZnO and identifying the factors affecting the PEDOT-PSS/MDMO-PPV/nc-ZnO/LiF/Al. By changing nc-ZnO by selectively suppressing the injection of

J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

performance of the cell. the ratio of MDMO-PPV/ZnO as 1:2 and 2:1 hole only one of the charge carrier was studied.The hole
and electron only devices were fabricated by mobility in the polymer phase of MDMO-PPV/nc-
suppressing electrons and holes respectively. The J–V ZnO (1:2 by wt) was found to be equal to the mobility
characteristic was studied. in prestine MDMO-PPV. It was found that the hole
mobility was not affected by the ZnO. By replacing
MDMO-PPV with a polymer of higher hole mobility
which combines with ZnO, higher efficiency solar
cells can be fabricated. Efficiency of 1.6% was
obtained [46].
16 Seok-Soon Kim Comparing the PV performance of hybrid solar cells The solar cells with a structure of flat TiO2 electrode, High efficiency (0.21%) was obtained for PV based on
et al. (2007) based on different nanostructures using TiO2 and random TiO2 np network and 2D TiO2 nanostructure ordered 2D TiO2 nanostructure owing to improved
MEH-PPV. were fabricated. charge transport and separation with large
interfacial area [47].
17 Date J.D. Moet Studying the limitation of HSC from mixture of The device structure used was ITO/PEDOT/PSS/Active The presence of highly reactive diethylzinc during
et al. (2007) dialkoxy-substituted PPV with precursor ZnO owing layer (MDMO-PPV:ZnO)/LiF/Sm/Al. The fabrication processing of BHJ of MDMO-PPV and ZnO caused the
to partial degradation of the polymer during was also made with P3HT:ZnO as active layer for polymer to degrade. HSC based on P3HT and ZnO had
processor. comparison. an estimated PCE of 1.4% [48].
18 Li Wang Fabricating multiarmed CdS nrs/MEH-PPV HSC. ITO coated glass was spin coated with the mixed Higher efficiency was obtained with pyridine (0.89%)
et al. (2007) solution of MEH-PPV and nc-CdS followed by than with chlorobenzene (0.14%). Thermal
thermal evaporation of Al. The active layer was treatments of the blend further enhanced the
processed in the solution of pyridine and efficiency to 1.17% [49].
chlorobenzene.
19 Zhijie Wang Fabricating MDMO-PPV capped PbS Q-dots solar cell. Blending of MDMO-PPV with MDMO-PPV capped The highest energy conversion efficiency (0.013%)
et al. (2008) PbS Q-dots as the active layer between anode (ITO) with the structure of ITO/PEDOT:PSS/MDMO-PPV/
and cathode (Al) and solar cells with different MDMO-PPV capped PbS Q-dots/Al was obtained [50].
annealing process were also discussed.
20 Li Yan Investigating the PV properties of MEH-PPV/TiO2 The structure of the cell followed was ITO/ MEH-PPV:TiO2 nanotubes had better PV properties
et al. (2008) nanocomposites. PEDOT:PSS/MEH-PPV:TiO2 (nps and nts than MEH-PPV:TiO2 nanoparticles [51].
respectively)/Al.
21 P. Suresh Investigating the optical and photovoltaic properties The solar cell was fabricated as follows ITO/ The efficiency of the solar cell 0.12% and 0.55% for
et al. (2008) of HSC based on blend of PPHT:ZnO and PPHT:ZnO/Al and also PPHT:ZnO prepared in PPHT:ZnO and PPHT:dye:ZnO respectively was
PPHT:dye:ZnO. different solvent. obtained, which enhances the photon absorption in
visible region. Increase in absorption and FL
quenching owing to incorporation of dye in
PPHT:ZnO composite was noticed. The effect of
solvent used for PPHT:ZnO layer was also studied
[52].
22 Mingqing Wang Fabricating of PPV/TiO2 hybrid composites from PPV The structure of the solar cell was ITO/PEDOT/PPV/ In sol–gel method TiO2 nanocomposites (40 wt%)
et al. (2008) precursor reaction in aqueous media. TiO2/Al. TiO2 introduced situ sol–gel approach and efficiency was high (0.018%) compared to direct
direct mixing method was adopted. mixing. The sol–gel method can be attributed to the
nanosized phase separation and direct mixing
attributed to the increase of the aggregation [53].

1231
 1232
Table 1 (Continued )

S. No. Author’s name Aim of the work Experimental details Author’s remarks

23 K. Vandewal Studying two modes of FTPS for a fast and highly (i) P3HT, PCBM and P3HT:PCBM active layers were The FTPS technique detected sub-band gap optical
et al. (2008) sensitive spectral characterization of organic and coated on to the PEDOT:PSS layer which was spin transition. In P3HT:PCBM blend, the sub-band gap
HSC. coated onto ITO glass. Al was the top electrode. absorption is dominated by formation of a ground
state charge transfer complex and no light could be
detected.
(ii) An aqueous citraperoxo – Ti(IV) gel precursor was The detected low energy bands in pure P3HT and in
spin coated onto FTO. After 650 8C heat treatment, P3HT/TiO2 junctions appeared after irradiation with
TiO2 was formed. P3HT layer was spin coated on top E > 1.9 eV [54].
to form 2 wt%. Gold act as the top electrode.
24 Yi-Ming Chang Introducing hydroxyl moiety onto P3HT to promote The photovoltaic device was prepared by spin P3HT:P3HT-OH:TiO2 was found to be more efficient
et al. (2008) polymer titanium interaction. coating PEDOT:PSS on ITO coated glass or PET than P3HT:TiO2 and P3HT-OH:TiO2 [55].
substrate, then the photoactive layers P3HT:TiO2,

J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

P3HT-OH:TiO2 and P3HT:P3HT-OH:TiO2 hybrid
solution was spin coated on the top of PEDOT:PSS. Al
was used as electrode.
25 Frederik C. Krebs Fabricating a nanostructured polymer solar cell ITO glass was spin coated with ZnO and the active The morphology of the device films and materials
et al. (2008) which operates in air. material used was P3CT/ZnO (P3CT was obtained characterized by TEM and X-ray scattering
from P3MHOCT). PEDOT:PSS and Ag were used as the techniques, showed that the particles were well
top electrodes. The experiment was performed in dispersed and quite homogeneous with respect to
inert and atmospheric conditions. particle size. The device performance was found to
improve in atmosphere [56].
26 Steven K. Hau Improving the stability by reversing the nature of ITO was coated on glass and plastic for comparison. The devices fabricated from the ZnO nps on ITO-
et al. (2008) charge collection using ZnO as electron selection Two types of device were fabricated conventional coated glass had an average PCE of 3.6%, which was
layer. device ITO glass/PEDOT:PSS/P3HT:PCBM/LiF/Al and very similar to that obtained from the high
inverted SC ITO glass/ZnO/P3HT:PCBM/PEDOT:PSS/ temperature processed sol–gel devices [57].
Ag.
27 I. Haeldermans Forming charge transfer complex (CTC) in P3HT:TiO2 The active device was prepared with ITO/PEDOT:PSS/ In the case of the P3HT:TiO2 blend, the energy of the
et al. (2008) BHJ SC. P3HT:TiO2/Ca/Al. The active layer P3HT:TiO2 was CT state was lower than both the band gaps of P3HT
prepared with various vol% of TiO2. Similar and TiO2, which implied that in this case, the CT state
fabrication was made with ZrO2. may be efficiently populated. In P3HT:ZrO2 blends,
however, the CT state was higher in energy than the
P3HT excitonic state, resulting in poor carrier
generations [58].
28 Johann Boucle Investigating BHJ SC based on TiO2 nr and P3HT. Blend film of TiO2:P3HT was spin coated onto glass Compared with the direct polarity where the ITO
et al. (2008) substrate followed by PEDOT:PSS. Al or Au was used electrode was used to collect holes, the reverse
for top metallic contact. The device structure for geometry used the dense TiO2 and PEDOT:PSS layers
direct polarity was ITO/PEDOT:PSS/blend/Al and for as hole and electron blocking layers respectively
reverse polarity ITO/dense TiO2/blend/PEDOT:PSS/ resulting in improved selectivity [59].
Au.
29 Serap Gunes Fabricating surface modified TiO2 np with 6PAA. The cell structure was ITO/PEDOT:PSS/TiO2:P3HT As the ratio of P3HT:TiO2/6PAA decreases, the
et al. (2008) (with different ratio)/LiF/Al. TiO2 nps surface was current increases slightly [60].
modified with 6PAA.
30 Jincheng Liu Studying MEH-PPV/TiO2 HSC using different ligands. The device structure was ITO/PEDOT:PSS/blend of TiO2 capped with TP resulted in higher PCE of 0.157%,
et al. (2008) MEH-PPV and TiO2 nrs/Al.TiO2 was capped with proving to be one of the best ligands for fabrication of
different ligands OLA, OPA and TP. HSC [61].
31 Qiquan Qiao Preparing HSC using buffer layer from water solution The structure of the device was FTO/TiO2 buffer A titanium buffer layer was introduced into an all
et al. (2008) processing. layer/TiO2/PTEBS blend/Au. The blend of the active water solution based BHJ polymer SC to improve
layer was done in water. interfacial contact. The efficiency improved was
quadrupled (0.04–0.17%) [62].
32 Michael Bredol Preparing hybrid SC with ZnS nanoparticles and The active layers of P3HT/ZnS:Mn blend (without I–V characteristic of a device with nanoparticles
et al. (2009) polymer. ZnS np and with 17 and 50 wt% of ZnS np) were spin content of 50 wt% reached a very high power
coated on ITO glass substrate with PEDOT:PSS. Al conversion efficiency of 0.2% compared to 17 wt%
was deposited as top electrode. and without ZnS nanoparticles [63].
33 Tsung-Wei Zeng Studying the performance of P3HT with The structure of ITO/PEDOT:PSS/P3HT:TiO2 PV performance having 0.83% PCE was obtained
et al. (2009) semiconductor TiO2 nanorods for use in polymer nanorods/TiO2 nanorods/Al was followed. owing to high molecular weight P3HT, High boiling
solar cell. point solvent trichlorobenzene and pyridine-
modified TiO2 nanorods [64].
34 Lung-Chein Chen Investigating the influence of dopant and polymeric ITO was coated on the glass to form anode substrate. PCE of 5.55% was obtained for the I2 based devices
et al. (2009) matrix on ITO/p-ZnPc/n-Si HSC. On n-type Si substrate, ZnPC + PMMA + I2 were due to the highest absorbance and the lowest
deposited. These substrates were sandwiched absorption edge exhibited by I2 doped ZnPC film at
between cathode material Al and anode. Different about 3.3 eV [65].
devices replacing iodine by aluminum chloride
hexahydrate, Magnese chloride and indium chloride
tetrahydrate were fabricated and results were
compared.
35 Ming-Chung Wu Studying the effect of molecular weight of P3HT and The solar cell was fabricated with structure ITO/ The device efficiency (0.61%) was improved by
et al. (2009) performance of P3HT:TiO2 nanorods by scanning PEDOT:PSS/P3HT:TiO2 nanorods/Al. increasing the molecular weight (66 kDa) of P3HT
probe microscope. due to the increase in both light harvesting and
carrier mobility [66].
Comparing device performance by varying PMMA The cell with a structure of ITO/PEDOT:PSS/P3HT/ The solar cell performance with PMMA
concentration is P3HT:TiO2 active layer. varying concentrations of PMMA:TiO2 nanorods/Al concentrations of (0.0, 1.6, 3.2, and 11.6 wt %) were
was fabricated. studied and it showed high PCE of (h = 0.65%) for

J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

1.6 wt% PMMA concentration is the active layer in
P3HT/PMMA:TiO2 blends [67].
36 Daqin Yun Comparing the performance of solar cell based on The solar cell was fabricated with a structure of ITO/ Improved device performance was obtained by
et al. (2009) MOPPV–ZnSe with and without incorporation of PEDOT:PSS/MOPPV–ZnSe/with and without PbSe/Al. incorporation of PbSe Q dots in active layer with PCE
PbSe nano crystal structure. of 0.14% [68].
37 Zhijie Wang Fabricating the HSC by using SnS nanoparticle. The hybrid device structures of ITO/PEDOT:PSS/ In P3HT based solar cells with 86 wt% SnS had good
et al. (2009) P3HT:SnS/Al and ITO/PEDOT:PSS/MDMO-PPV:SnS/ efficiency (0.01%) and MDMO-PPV with 67 wt% SnS
Al were fabricated for comparison. proved an efficiency of 0.02% [69].
Fabricating the HSC MDMO-PPV capped PbS The solar cell was fabricated with a structure of ITO/ The solar cell performance was optimized and the
nanorods. PEDOT:PSS/MDMO-PPV:PbS nanorods/Al. influence of ambience, annealing process and
nanorods content was analysed. 75 wt% PbS content
solar cell offered the best performance compared to
others [70].
38 Chin-Yi Liu Fabricating the HSC based on blends of Si ncs and The solar cell was fabricated with structure ITO/ The Si ncs size decreased with increasing PV
et al. (2009) P3HT. PEDOT:PSS/Si ncs:P3HT/Al. properties. Roughly 35 wt% of Si ncs produced the
best PV devices with 1.15% PCE [71].
39 Chen-Yu Chou Studying the lengthening of solidification time to The structure of the solar cell was ITO/ZnO film/ZnO For the longest drying time of the device PCE (3.58%)
et al. (2009) improve PCE of polymer/ZnO nanorod HSC. nanorod/P3HT:PCBM/Ag. was high compared to fast dried device, owing to
crystallinity of the polymer and infiltration of the
photo active layer [72].
40 Golap Kalita Demonstrating hybrid solar cells using Si nws and Silicon nanowires were fabricated on Si wafer. P3OT The incorporation of functionalized MWNTs along
et al. (2009) polymer incorporating MWNTS. and P3OT:OMWNTS were drop casted over with the polymers showed considerably enhanced
nanowires. Au was used as working electrode. device performance owing to improved hole
mobility. The fabricated device with the structure
Au/P3OT + O-MWNTs/n-Si nws marked a conversion
efficiency of 0.61% [73].
41 Yun-Yue Lin Demonstrating red light harvesting owing to P3HT/ The structure of HSC was ITO/PEDOT:PSS/P3HT:FeS2 The PCE of the device was 0.16%. The result
et al. (2009) FeS2 nanocrystal. hybrid/Al. demonstrated that the adding of FeS2 ncs in P3HT can
contribute to the extended photovoltaic response in
the red light region, which can act as a potential
candidate for the polymer/inorganic hybrid solar cell
application [74].
42 Deepak Verma Studying the characteristics of blend solution having The active materials used were ITO/PEDOT:PSS/ The hybrid layers deposited with CdTe and MEH-PPV
et al. (2009) proper dispersion of surfactant free CdTe np with CdTe/MEH-PPV/Al. Spin coating technique was used. with weight ratio 40:3 indicated proper dispersion of
MEH-PPV. CdTe and MEH-PPV were taken in different ratios for nanoparticles and proved higher PCE of 0.06% [75].
the study.
43 Akihiro Takeda Investigating Cd free inorganic hybrid solar cells with Bilayer and BHJ cells were fabricated using CIS and The efficiency of BHJ proved to be Higher (8  104)
et al. (2009) CuInS2 and C60. C60 as active layer as follows: FTO glass/PEDOT:PSS/ than bilyer (6  104) owing to increase in
CIS/C60/Al and FTO glass/PEDOT:PSS/CIS:C60/Al. photoelectron conversion area [76].
44 Junpeng Liu Demonstrating HSC based on vertically oriented ZnO Devices are fabricated with different ZnO nw The efficiency was found to increase by incorporating
et al. (2009) nws and organic molecular materials. diameter, length and organic layer thickness ITO/ ZnO nws. The PCE was maximum for a device with
ZnO/ZnO nw/CuPC:C60/CuPc/PEDOT:PSS/Au. smaller thickness 20 nm diameter and length 100 nm
which had enough space to allow the organic layers
to infiltrate the space between the ZnO nws. The PCE

1233
was 0.53% [77].
 1234
Table 1 (Continued )

S. No. Author’s name Aim of the work Experimental details Author’s remarks

45 Vladimir Svrcek Investigating the photoelectric property of BHJ SC Two different studies were made to analyse I–V characteristic enhanced when BHJ was
et al. (2009) based on Si-ncs and P3HT. photoconductivity property of BHJ: introduced into TiO2 nt. The arrangement of Si-ncs/
(a) Parallel conductivity was investigated using Si- P3HT BHJ within ordered TiO2 nt perpendicular to
ncs/P3HT blend coated on platinum contact the contact facilitated excition separation and charge
evaporated on glass. transfer along nts [78].
(b) For perpendicular conductivity materials used in
fabrication were TCO coated glass/PEDOT:PSS/Si-
ncs:P3HT/TiO2 nts. Si-ncs/P3HT blend was
incorporated into TiO2 nts.
46 Alejandro L. Briseno Demonstrating the SC based on P3HT and QT with The device was fabricated using Pristine ZnO, ZnO/ Oligo and polythiophene were grafted onto ZnO nw
et al. (2010) ZnO single nw. P3HT composites and ZnO/QT composite. to produce p–n heterojunction. The efficiency of
ZnO/P3HT composite was found to be high (0.036%

J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

compared to other devices [79].
47 Smita Dayal Fabricating BHJ SC with CdSe tetra pods and low ITO coated glass was coated with PEDOT-PSS BHJ solar cell of 3.13% was obtained. Low band gap
et al. (2010) band gap polymer. followed by spin coating the active layer polymer played an important role for better solar
CdSe:PCPDTBT (9:1 wt. ratio). Al was used as the spectrum harvesting and contribution of np towards
working electrode. achieving high PCE [80].
48 Kaushik Roy Choudhury Demonstrating solution processed hybrid polymer PEDOT:PSS was spin coated onto ITO glass with Investigation of the optimizated device based on
et al. (2010) nc-IR LEDs with enhanced efficiency using PbSe ncs active layer prepared with blend of PbSe ncs and nanocomposites blend architecture was achieved
in polymer. MEH-PPV in cholorobenzene in various proportions. with maximum EQE of 0.83% at a peak emission wave
BCP was thermal evaporated on active layer followed length of 1280 nm [81].
by evaporation of LiF/Al.
49 Tzong-Liu Wang Investigating electrochemical and photochemical ITO/PEDOT:PSS/active layer P3HT:CdSe-OH or The performance of the device P3HT:CdSe–PVK
et al. (2010) properties of HSC using CdSe–PVK composite. P3HT:CdSe–PVK (1:1 wt ratio)/Al were the device blend was found to be significant in composition
structure. with P3HT:CdSe–OH showing efficiency of 0.02%
[82].
50 Jun Yan et al. (2010) Electropolymerizing PEDOT:PSS films on ITO glass in ITO/PEDOT/ZnO:MDMO-PPV 1:2 ratio/Al. PEDOT Electrochemical polymerization process gave higher
BFEE with three electrode system. was prepared with electrolysis of trielectrode where conversation efficiency (0.33%) when compared to
pt acts as counter electrode, ITO glass as working and the spin coating technique [83].
Ag/AgCl electrode as reference electrode. ITO and Ag/
AgCl were kept parallel in the cell during
polymerization process. The electrolytic solution
was EDOT in BFEE.
51 Minas M. Stylianakis Modifying of SWCNT with thiophene. ITO substrate was coated with PEDOT:PSS followed Modified SWCNT was incorporated, which contains
et al. (2010) by spin coating of three different photoactive layers pendant thiophene rings into polymer/fullerene PV
(a) P3HT–PCBM device. Polymer/fullerene cell with SWCNT CONHTh
(b) SWCNT doped P3HT:PCBM/P3HT:PCBM and was found to be superior to other devices achieving
(c) SWCNT-CONHTh doped P3HT:PCBM the efficiency 1.78% owing to an extention of the
Al was used as electrode. excition, dissociation area and to faster electron
transfer than nt [84].
 J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238 1235

(ii) Open-circuit voltage (Voc): When the cell is operated at open to its stability. PEDOT:PSS is the often used hole transporting layer,
circuit, I = 0 and the voltage across the output terminals is but a few researchers have used TiO2 as charge transport complex
defined as the open-circuit voltage. (CTC) acting as an intermediate state in charge separation and
  recombination in order to enhance the device performance. PEDOT
kT IL
V oc ¼ ln þ1 is another material used for the same purpose. In the active layer
q IO
many works have been carried out. The following are the points to
(iii) Short-circuit current (Isc): When the cell is operated at short be noted.
circuit, V = 0 and the current I through the terminals is defined
as the short-circuit current. 1. Lower band gap polymers with a broad absorption spectrum
ISC  IL increases PCE owing to higher solar spectrum harvesting.
2. Incorporating CdSe np enhances the thermal stability of PVK.
(iv) Maximum power point (MPP): (Impp, Vmpp) on the I–V curve 3. Chemical combination of single or multiwalled CNT, addition of
is the point where maximum power is produced. Power (P) is ZnO nws incorporated into polymer attributes to an extension of
the product of current and voltage (P = IV) and is illustrated in excitation dissociation area and a faster electron transfer.
the Fig. 2 as the area of the rectangle formed between a point 4. Addition of FeS2 ncs in P3HT extends the PV response in red light
on the I–V curve and the axes. The maximum power point is region.
the point on the I–V curve where the area of the resulting 5. Introduction of optical spacers like TiOx invole multiple
rectangle is largest. reflection leading to higher performance.
(v) Fill factor (FF): This is the ratio of the maximum power point 6. Lengthening of solidification time of active layer increases the
to the product of open circuit voltage (Voc) and the short PCE.
circuit current (Isc):
Pm h  AC  E
FF ¼ ¼
V OC  ISC V OC  ISC In general many cathode materials were used but Al was the
mostly preferred one. Some researchers worked with optimized
(vi) Power conversion efficiency (PCE or he): The ratio of power
weight ratio of the donor and acceptor, suitable solvent for
output to power input. In other words, PCE measures the
blending of the active layer, changing the different electrode and
amount of power produced by a solar cell relative to the
varying the donor or acceptor concentration. Many experimental
power available in the incident solar radiation (Pin). Pin here is
comparative works have been done between BHJ and bilayer
the sum over all wavelengths and is generally fixed at
device.
1000 W/m2 when solar simulators are used.
In the hybrid solar cells polymer materials acting as donors are
P OUT V OC ISC P3HT, PPHT, P3OT, P3BT, MDMO-PPV, MEH-PPV, MOPPV etc., and
hAM1:5 ¼ ¼ FF
PIN P IN inorganic materials used as acceptors are TiO2, ZnO, PbS, ZnS, CdS,
(vii) Quantum efficiency (QE): It refers to the percentage of SnS, CIS, PbSe, CuPc, PS, Si nws, Si ncs, etc. Among these donors and
photons that are converted into electric current (i.e., collected acceptors, P3HT proved to be one of the best donors and TiO2, ZnO
carriers) when the cell is operated under short circuit and Si acted as good acceptors. By reversing the nature of charge
conditions. collection using ZnO as an electron selection layer [57], lengthen-
 External quantum efficiency: External quantum efficiency ing of solidification time [72], using I2 dopants [65], CdSe
(EQE) is the fraction of incident photons that are converted to tetrapodes and low band gap polymer [80] higher efficiency can
electrical current, while internal quantum efficiency (IQE) is the be achieved.
fraction of absorbed photons that are converted to electrical
current. 6. Conclusion
 Internal quantum efficiency: Internal quantum efficiency is
related to external quantum efficiency by the reflectance (R) and Increasing consumption of electric power and effect of global
the transmittance (T) of the solar cell by warming have deviated researchers towards alternative pollution
free natural sources from fossil fuels. One such field of conversion
EQE of solar energy into electric energy plays a vital role in research,
IQE ¼ technology and domestic power consumption. Efforts in the last
ð1  R  TÞ
decade have led to number of new technologies to increase the
efficiency. One such grown field is the hybrid solar cell in
4. Review of hybrid solar cell particular, where blend of organic/inorganic is used for charge
separation. The various methods of blending, using nanotubes or
This review aims to summarize the recent approaches to nanoparticles, have raised the performance of the cell. Different
fabricate the HSC in different combinations of organic and techniques of coating active layers change the morphology, which,
inorganic materials and their efficiency. In this article a total of in turn, affects the conversion output. Use of buffer layers and
84 papers have been referred to, among which 53 have been optical spacers further enhances the efficiency. The focus of the
summarized in Table 1, in terms of names of authors’ (reference), recent research on this blending technique of active layers has
aims of their works, approaches to their works (materials used/ raised the cell efficiency above 5%. This review helps in the further
experimental details) and authors conclusions (reports). The improvement of the device performance for the selection of
essence of this analysis will be a delightful treat for the budding suitable material with proper band gap and knowing other factors
researchers in order to understand HSC. that affect efficiency.

5. Results and discussion Acknowledgement

The above details lead to the following discussion: The two of us (J.C and D.N) gratefully acknowledge the financial
Anode material used is glass or plastic coated with either of ITO, support from the UGC, Government of India for the major research
FTO, GZO, etc., but in general ITO coated glass is mostly used owing project (F-33-19/2007(SR)).
1236 J. Chandrasekaran et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1228–1238

Appendix A PCBM (a) 1-((3-methoxycarbonyl)-prop-1-yl)-1-phenyl (6,6)

C61; (b) [6,6]-phenyl-C61-butyric-acid methyl ester
Ac Surface area of the solar cell PCPDTBT Poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta (2,1-
AFM Atomic Force Microscopy b; 3,4-b0 ) dithiophene)-alt-4,7-(2,1,3-benzothiadia-
Ag Silver zole))
Al Aluminium PEDOT:PSS Poly(3,4-ethylenedioxythiophene):poly(styrenesulfo-
AS Aqueous soluble nate)
Au Gold PPHT Poly-3-phenyl hydrazones thiophene
BCP Bathocuprine PTEBS Poly[2-(3-thienyl)-ethoxy-4-butylsulfonate]
BFEE Boron trifluoride diethyl etherate electrolyte PV Photovoltaic
CdSe Cadmium selenide PVK Poly-vinyl carbazole
CIS Copper indium sulfide q Elementary charge
CISe Copper indium diselenide Q-dots Quantum dots
CT Charge transfer QT Quarterthiophene
CuInS2 Copper indium sulfide RH Relative humidity
CTC Charge transport complex Sm Samarium
E Input light irradiance SnO2 Tin oxide
ECE Energy conversion efficiency SnS Tin sulfide
EDOT 3,4-Ethylenedioxythiophene SWCNT Single walled carbon nano tubes
FeS2 Iron disulphide T Absolute temperature
FL Fluorescence TCO Transparent conductive oxide
FTPS Fourier-Transform Photocurrent Spectroscopy TiO2 Titaniumdioxide
FTO Fluorine doped tin oxide TOPO Trioctylphosphine oxide
HgTe-AS Mercury telluride – aqueous soluble TP Thiophenol
HgTe-OS Mercury telluride – organic solvent Voc Open circuit voltage
HSC Hybrid solar cell wt weight
IL Photogenerated current (A) ZnO Zinc oxide
I0 Reverse saturation current (A) ZnPc Zinc phthalocyanine
I2 Iodide ZnS Zinc sulfide
IR LED Infra red light emitting diode ZrO2 Zirconium dioxide
ITO Indium tin oxide 6PAA 6-palmitate ascorbic acid
k Boltzmann’s constant h Efficiency
LiF Lithium fluoride
MDMO-PPV Poly[2-methoxy-5-(30 70 -dimethyloctyloxy)-1,4-phe-
nylene vinylene]
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