``

QUANTUM DOT SOLAR CELLS

[REPORT SUBTITLE]

Vikash Keshav (CUJ/I/2013/INT/017)

Md. Shahbaz Hussain (CUJ/I/2013/INT/027)
Saif Kamal (CUJ/I/2013/INT/015)

ACKNOWLEDGEMENT
We have taken efforts in this project. However, it would not
have been possible without the kind support and help of
many individuals. We would like to extend our sincere
thanks to all of them.
We are highly indebted to Dr. Lawrence Kumar for
providing this golden opportunity to work on this project
and for providing guidance and constant supervision as
well as for providing necessary information regarding the
project & also for the support in completing the project.
Our thanks and appreciations also go to all the people who
have willingly helped us out with their abilities.

PAGE 1

CONTENT
1.
2.
3.
4.

Keywords
Introduction
Quantum Confinement Effect for QDSCs
Nanocrystalline Photoelectrodes For Solar Cells

5.
6.
7.
8.

Fabrication
Suggested Improvement
Summary and Future Work
References

KEY WORDS

CBD Chemical Bath Deposition

DSC Dye-sensitized solar cell

EHP Electron-Hole Pair

PAGE 2

ITO Indium Tin Oxide

FTO Fluorine doped tin oxide

MEG Multiple Electron Generation

PV Photovoltaic

QD Quantum Dot

QDSC Quantum dot sensitized solar cell

SILAR Successive Ionic Layer Adsorption and Reaction

UV Ultraviolet

Eg Energy gap

INTRODUCTION
The establishment of low-cost and high-performance solar cells for
sustainable energy sources to replace fossil fuels has become an
urgent subject to scientists around the world. Because traditional
photovoltaic devices (i.e. the p-n junction silicon crystalline solar cells)
suffer from high costs of manufacturing and installation, now the focus
is on the next generation of solar cells with high efficiency at
economically viable costs. As a cost-effective alternative to siliconbased photovoltaics, semiconductor quantum dot (QD)-sensitized solar
cells (QDSCs) have attracted considerable attention recently and have
shown promising developments for the next generation of solar cells.

PAGE 3

QDSCs can be regarded as a derivative of dye-sensitized solar cells

(DSCs), which were first reported by ORegan and Gratzel in 1991. In
DSCs, the sensitizer commonly uses organic dyes of ruthenium
polypyridine complexes.
To increase the light harvest in the visible light region many efforts
have been made to focus on the development of high-performance
sensitizers. It has always been a challenge to obtain an ideal organic
dye as a sensitizer to absorb photons in the full sunlight spectra. For
this reason, narrow-band-gap semiconductor QDs, such as CdS, CdSe,
PbS, and InAs, have been used as the photosensitizer instead of
organic dyes due to their versatile optical and electrical properties,
including:
1) A tunable band gap depending on the QD size,
2) A larger extinction coefficient,
3) Higher stability toward water and oxygen, and
4) Multiple exciton generation (MEG) with single-photon absorption.
The theoretical photovoltaic conversion efficiency of QDSCs can reach
up to 42% in view of the MEG effect of QDs. Such efficiency is much
higher than the rate of 31% for semiconductor solar cells according to
the Schockley-Queisser limit.

FIG-a) Schematic illustration of the structure of a quantum

dotsensitized solar cell (QDSC); and
(b) Schematic illustration of photo induced charge transfer
processes following a laser pulse excitation.

PAGE 4

Figure 1(a) shows the cell structure of a QDSC, which consists of a

wide-band-gap mesoporous oxide film (a photoelectrode, such as the
commonly used TiO2 or ZnO), QDs (the sensitizer), an electrolyte, and
a counter electrode.
During operation, photons are captured by QDs, yielding electronhole
pairs that are rapidly separated into electrons and holes at the
interface between the nanocrystalline oxide and QDs. The electrons
jump into the oxide film, and the holes are released by redox couples in
the electrolyte.
Figure 1(b) shows photo induced charge transfer processes employing
S2/Sn2 as the redox couple:
1) Charge injection from an excited QD into TiO2,
2) Transport of electrons to the collecting electrode surface,
3) Hole transfer to the redox couple,
4) Regeneration of the redox couple,
5) Recombination of electrons from the QD and the oxidized form of
the redox couple, and
6) Interfacial recombination of electrons from TiO2 and the oxidized
form of the redox couple.
Prashant Kamat groups works reported that the electron transfer
between QD and TiO2 was an ultrafast process with a rate constant of
the order of 10^10-10^11s, which was faster than that of hole transfer
10^7-10^9s.
However, electron transport within the mesoporous TiO2 film is slower
than that of electron and hole transfers. So the recombination losses
become a major factor in limiting the overall efficiency.

PAGE 5

Quantum confinement effect for

QDSCs
QDs are extremely small semiconductor nanocrystals with a size
comparable to the Bohr radius of an exciton. For most semiconductors,
the Bohr radius of an exciton is in the range of 110 nm: for example, it
is 4.2 nm for Si, 3.1 nm for CdS, 6.1 nm for CdSe, and 2.2 nm for ZnO.
However, the Bohr radius of the exciton is very large for some
semiconductors: it is 20.4 nm for PbS, 46 nm for PbSe, and 67.5 nm for
InSb. Due to the dimension effect, the behavior of electrons in QDs
differs from that in the corresponding bulk material, which is called the
quantum confinement effect. A semiconductor with a larger excitonic
Bohr radius means that the QDs made from the material may achieve
a strong confinement effect more easily. Because of the quantum
confinement effect, the band gap energy (Eg) of QD increases with the
decrease of particle size. Eg can be elucidated by Eg 81/r2, where r is
the radius of QD. The increase of Eg means that more energy will be
needed in order to be absorbed by the QD. So the range of optical
absorption wavelengths of QD can be tuned by controlling the size of
QD. Such a feature of QDs with tunable Eg has led to their applications
in light-emitting diodes (LEDs) for full-color displays, and in QDsensitized solar cells for the generation of optical absorption at desired
wavelengths.
For QDs, the increase of band gap would be expected to have
favorable conduction band energies for injecting electrons into a
photoelectrode. However, the increase of Eg indicates that only high
energy photons can be absorbed by the QD, leading to the absorption
wavelength edge of the QD blue shift. Too small QDs will lead to too
much low the optical absorption for the photoelectrodes, which has
negative impacts on the solar cells. Therefore, the best solar to
electricity conversion efficiency can be obtained by optimizing the
band energy structure of QDs to match the oxide film and obtain a
wide optical absorption wavelength. The energy band parameters of
QDs and oxides, which are usually chosen to fabricate QDSCs. The
principles for choosing materials to construct solar cells are as follows:
1) Optical absorption is primarily determined by the band gap of active
materials, and therefore the materials with narrow and direct band
gaps are preferred; and

PAGE 6

2) The device structure should be designed by choosing materials with

well-matched energy levels that may establish a suitable energy
gradient, allowing the charges to transport highly efficiently within the
solar Cell.

Solutions of quantum dots of varying size. Note the variation in color of

each solution illustrating the particle size dependence of the optical
absorption for each sample. Note that the smaller particles are in the
blue solution (absorbs blue), and that the larger ones are in the red
(absorbs red).

PAGE 7

Nanocrystalline Photoelectrodes For Solar Cells

As wide-band-gap semiconductors for the sensitizer scaffold,
conventional TiO2 and ZnO porous nanocrystalline films had been used
in QDSCs due to the large surface area available for QD adsorption.
TiO2 is commonly chosen as the photoelectrode of QDSCs, and it
exhibits high power conversion efficiency (about 5%). For example, the
research of Hossain et al. showed that CdSe sensitized TiO2 solar cells
incorporating light-scattering layers presented a power conversion
efficiency of 5.21%. Kamat et al. reported that QDSCs with Mn-doped
CdS CdSe on the TiO2 film achieved a power conversion efficiency of
5.4% (3). Lee et al. (47) developed a PbSHg QD-sensitized TiO2 solar
cell with an unprecedentedly high power conversion efficiency of 5.6%.
ZnO is a good alternative to TiO2because it possesses energy-band
structure and physical properties that are similar to those of TiO2. But
it has an electronic mobility 4 times higher than that of TiO2.
In addition, ZnO is easy to form anisotropic structures (such as
nanowires, nanorods, and nanotubes), which presents unique
electronic and optical properties. Furthermore, a photoelectrode film
constructed with these nanostructures is helpful for the distribution of
QDs (25). ZnO nanostructured photoelectrodes for QDSCs have been
investigated over the last several years. However, the efficiency of
ZnO-based QDSCs is lower than that of TiO2-based devices, which is
likely due to the high surface charge recombination in ZnO. The high
surface charge recombination can be attributed to many defects of the
ZnO surface.
In addition, the chemical stability of ZnO is less than that of TiO2,
which makes it easy for ZnO to react with the electrolyte. Tian et al.
(61) developed a facile passivation strategy for ZnO mesoporous
photoelectrodes. This method not only opened the apertures to
improve the distribution of QDs in the photoelectrodes, increased the
specific surface area, and reduced the surface defects of the ZnO
photoelectrodes to accommodate more QDs, but also suppressed the
charge recombination and prolonged the electron lifetime by

PAGE 8

introducing a barrier layer. As a result, a record power conversion

efficiency of 4.68% for ZnO-based QDSCs was obtained.
Figure (a) and (b) show the transmission electron microscopy (TEM)
and high-resolution TEM images of the passivated ZnO loaded with
QDs, showing the passivated ZnO coated by TiO2and CdS-CdSe QDs
that are 4-6nm in size. In addition, this passivation strategy can also be
applied in ZnO nanowires to enhance their performance (as shown in
Fig. (c)-(f)).

PAGE 9

Fabrication
Materials
Cd(CH3COO)2.2H2O (99%), KCl, Na2S, Zn(NO3)2, Se powder, S
powder, Na2SO3, TiCl4, TiO2 paste, FTO (Fluorine-doped tin oxide).

Preparation on sensitized TiO2 films

The TiO2 films were coated by layers TiO2 by silk-screen printing. The
TiO2 films were annealed at 500C for 30 min. Their sizes ranged from
10 to 30 nm. The thickness of TiO2 films was around 4 m measured
by Stylus spectra. Then, the TiO2 film was dipped in 40-mmol TiCl4
solution for 30 min at 70C and sintered at 500C for 30 min. The specific
surface area of the mesoporous TiO2 was investigated by using the N2
adsorption and desorption isotherms before and after the calculation.
The surface area is 120.6 m2g1 (measured by BET devices). This
result indicates that the synthesized material has wider mesoporous
structure.

Preparation TiO2/CdS/CdSe/ZnS films

The TiO2/CdS/CdSe/ZnS films were synthesized by SILAR method as
follow:
Firstly, the TiO2 film was dipped in 0.5 M Cd2+ -ethanol solution for 1
min and rinsed with ethanol. Then, it was dipped for 1 min in 0.5 M S
2--methanol solution and rinsed with methanol after drying in the air (a
cycle SILAR). Amount of CdS QDs was increased by repeating the
assembly cycles from one to five cycles. The secondly, the TiO2/CdS
was dipped into 1M Cd2+ -ethanol solution for 1 min at room
temperature and rinsed with ethanol. Then, it was dipped for 1 min in
0.5 M Se 2aqueous solution and rinsed with pure water after drying
in the air (a cycle SILAR). Amount of CdSe QDs was increased by
PAGE 10

repeating the assembly cycles from one to five cycles. For the ZnS
passivation layer, the TiO2/CdS/CdSe films were dipped into 0.1 M Zn
2+ -solution and 0.1 M S 2--solutions for 1 min and rinsed with pure
water between two dips (a total of two cycles). Finally, it was annealed
in a vacuum environment with different temperatures to avoid
oxidation. The TiO2/CdS/CdSe/ZnS was being measured thickness by
the Stylus spectra. The results of the average thickness of the CdS (3
cycles), CdSe (3 cycles), ZnS (2 cycles) are 351.9 nm, 56.1nm, 257.8
nm respectively. The coating of F ions was performed by dipping the
TiO2 photoelectrode into a 1 M NH4F aqueous solution for 2 min, rinsed
by de-ionized water. Two layers of F ions were coated: the 1st was
coated before the deposition of CdS QDs, the second after the
deposition of three layers of QDs and the same for CdSe.

Fabrication of QDSSCs
The structure of QDSSCs was designed by the photoanodes and
counter electrodes using a Surlyn at 170C. The electrolyte was filled
from a hole made on the counter electrode. The active area of QDSSCs
was 0.38 cm2. The polysulfide electrolyte was 0.5 M Na2S, 0.2 M S and
0.2 M KCl in Milli-Qultrapure water/methanol (7:3 by volume).

PAGE 11

Suggested Improvement
MEG in QDs has been considered another way to enhance the power
conversion efficiency of QDSCs by utilizing the excess energy in the
absorbed photons. The MEG effect is that two or more electron-hole
pairs (excitons) are generated by one photon excitation, in contrast
with the conventional case where one photon excitation can produce
only a single exciton. In theory, the MEG effect requires a photon with
energy at least twice that of the band gap of the QDs. In view of the
MEG effect, the theoretic power conversion efficiency of QDSC has
been predicted to be as high as 42%, which is higher than the
Shockley-Queisser efficiency limit of 31%, for the traditional singlejunction solar cells.
The experimental study of Semonin has proven the feasibility of this
concept, with the demonstration of an external quantum efficiency
greater than 100% at wavelengths below 400 nm on a p-n junction
solar cell. So the utilization of high-energy photons to generate
multiple excitons or capture hot electrons before their thermalization
can boost the operational efficiency of QDSC. The MEG effect is a
phenomenon that can also be observed in a bulk semiconductor.
However, the required threshold for the energy of photons is much
higher than that in QDs. The possibility of enhanced MEG in QDs was
first proposed in 2001. The possible reasons for the MEG effect, which
can be achieved easily in QDs, have been attributed to the following:
1) The electron-hole (e-h) pairs are correlated and thus exist as
excitons rather than free carriers;
2) The rate of hot electron and hole cooling can be slowed because of
the formation of discrete electronic states;
3) Momentum is not a good quantum number, and thus the need to
conserve crystal momentum is relaxed; and

PAGE 12

4) Auger processes are greatly enhanced because of the increased e-h

Coulomb interaction. So the production of multiple exciton pairs in QDs
can be enhanced in comparison with bulk semiconductors.
MEG in QDs is a very important process that, if harnessed, can lead to
a new solar conversion efficiency limit. Although reasonably high and
reliable MEG efficiencies have now been reported, no QD-based solar
cells have yet shown enhanced conversion efficiency due to MEG
effects. So the achievement of QD solar cells with MEG effect
enhancement is still facing a huge challenge, partially because the
excitation of the MEG effect requires photons with relatively high
energy and a pump light with high power density. To make the largest
impact on solar energy technologies, the MEG efficiency needs to be
further improved so that the onset of MEG occurs as close to 2Eg as
possible.

PAGE 13

Summary and Future Work

Semiconductor QDs have been drawing great attention recently as a
material for solar energy conversion due to their high absorption
coefficient, quantum confinement (tunable band gap), and MEG
effects. QDSCs are burgeoning semiconductor QD solar cells that show
promising developments for the next generation of solar cells. Future
works should focus on improving the performance of the solar cells as
follows:
1) Designing new semiconductor QDs with a large wavelength range of
optical absorption in terms of quantum confinement;
2) Getting MEG effect enhancement of QDs by reducing the threshold
energy; and
3) Constructing suitable porosity for photoelectrodes to load more QDs
and decrease the charge recombination.
However, QDSCs are still in their infancy and face huge challenges in
their development. With the recent advances in the study of
semiconductor QDs, we expect major breakthroughs in developing
QDSCs in the future.
PAGE 14

References
1. Graetzel M, Janssen RAJ, Mitzi DB, Sargent EH. Materials interface
engineering for solution-processed photovoltaics. Nature 2012; 488:
30412.
2. Tada H, Fujishima M, Kobayashi H. Photodeposition of metal sulfide
quantum dots on titanium(IV) dioxide and the applications to solar
energy conversion. Chem Soc Rev 2011; 40:423243.
3. Santra PK, Kamat PV. Mn-doped quantum dot sensitized solar cells: a
strategy to boost efficiency over 5%. J Am Chem Soc 2012; 134:
250811.
4. Hossain MA, Jennings JR, Koh ZY, Wang Q. Carrier generation and
collection in CdS/CdSe-sensitized SnO2 solar cells exhibiting
unprecedented photocurrent densities. Acs Nano 2011; 5: 317281.
5. Ryu J, Lee SH, Nam DH, Park CB. Rational design and engineering of
quantum-dot-sensitized TiO2 nanotube arrays for artificial
photosynthesis. Adv Mater 2011; 23: 18838.
6. Sugaya T, Numakami O, Oshima R, Furue S, Komaki H, Amano T, et
al. Ultra-high stacks of InGaAs/GaAs quantum dots for high efficiency
solar cells. Energy Environ Sci 2012; 5:62337.

PAGE 15

7. Kamat PV. Quantum dot solar cells. The next big thing in
photovoltaics. J Phys Chem Lett 2013; 4: 90818.
8. Oregan B, Gratzel M. A low-cost, high-efficiency solar-cell based on
dye-sensitized colloidal TiO2films. Nature 1991; 353: 73740.
9. Bessho T, Yoneda E, Yum JH, Guglielmi M, Tavernelli I, Imai H, et al.
New paradigm in molecular engineering of sensitizers for solar cell
applications. J Am Chem Soc 2009; 131: 59304.
10. Bomben PG, Robson KCD, Sedach PA, Berlinguette CP. On the
viability of cyclometalated Ru(II) complexes for light-harvesting
applications. Inorg Chem 2009; 48: 963143.
11. Johansson PG, Rowley JG, Taheri A, Meyer GJ. Longwavelength
sensitization of TiO2 by ruthenium diimine compounds with low-lying
pi* orbitals. Langmuir 2011; 27: 1452231.
12. Zhao HC, Harney JP, Huang YT, Yum JH, Nazeeruddin MK, Gratzel M,
et al. Evaluation of a ruthenium oxyquinolate architecture for dyesensitized solar cells. Inorg Chem 2012; 51:13.
13. Kim J, Choi H, Nahm C, Moon J, Kim C, Nam S, et al. The effect of a
blocking layer on the photovoltaic performance in CdS quantum-dotsensitized solar cells. J Power Sources 2011; 196: 1052631.
14. Panigrahi S, Basak D. Morphology driven ultraviolet photosensitivity
in ZnO-CdS composite. J Colloid Interface Sci 2011;364: 107.
15. Robel I, Subramanian V, Kuno M, Kamat PV. Quantum dot solar
cells. Harvesting light energy with CdSe nanocrystals molecularly
linked to mesoscopic TiO2 films. J Am Chem Soc 2006; 128: 238593.
16. Shen Q, Kobayashi J, Diguna LJ, Toyoda T. Effect of ZnS coating on
the photovoltaic properties of CdSe quantum dotsensitized solar cells. J
Appl Phys 2008; 103: 084304.
17. Plass R, Pelet S, Krueger J, Gratzel M, Bach U. Quantum dot
sensitization of organic-inorganic hybrid solar cells. J Phys Chem B
2002; 106: 757880.
18. Yu P, Zhu K, Norman AG, Ferrere S, Frank AJ, Nozik AJ.
Nanocrystalline TiO2 solar cells sensitized with InAs quantum dots. J
Phys Chem B 2006; 110: 254514.

PAGE 16

19. Bang JH, Kamat PV. Solar cells by design: photoelectrochemistry of

TiO2 nanorod arrays decorated with CdSe. Adv Funct Mater 2010; 20:
19706.
20. Gonzalez-Pedro V, Xu X, Mora-Sero I, Bisquert J. Modeling highefficiency quantum dot sensitized solar cells. Acs Nano 2010; 4:
578390.
21. Yu X-Y, Liao J-Y, Qiu K-Q, Kuang D-B, Su C-Y. Dynamic study of highly
efficient CdS/CdSe quantum dot-sensitized solar cells fabricated by
electrodeposition. Acs Nano 2011; 5:9494500.
22. Cheng CW, Karuturi SK, Liu LJ, Liu JP, Li HX, Su LT, et al. Quantumdot-sensitized TiO2 inverse opals for photoelectrochemical hydrogen
generation. Small 2012; 8: 3742.
23. Zhu G, Pan L, Xu T, Sun Z. CdS/CdSe-cosensitized TiO2 photoanode
for quantum-dot-sensitized solar cells by a microwave-assisted
chemical bath deposition method. Acs Appl Mater Inter 2011; 3:
314651.
24. Lee YL, Lo YS. Highly efficient quantum-dot-sensitized solar cell
based on Co-sensitization of CdS/CdSe. Adv Funct Mater 2009; 19:
6049.
25. Tian JJ, Gao R, Zhang QF, Zhang SG, Li YW, Lan JL, et al. Enhanced
performance of CdS/CdSe quantum dot cosensitized solar cells via
homogeneous distribution of quantum dots in TiO2film. J Phys Chem C
2012; 116: 1865562.
26. Kamat PV. Quantum dot solar cells. Semiconductor nanocrystals as
light harvesters. J Phys Chem C 2008; 112: 1873753.
27. Tvrdy K, Frantsuzov PA, Kamat PV. Photoinduced electron transfer
from semiconductor quantum dots to metal oxide nanoparticles. Proc
Natl Acad Sci U S A 2011; 108: 2934.
28. Chakrapani V, Baker D, Kamat PV. Understanding the role of the
sulfide redox couple (S2-/S-n(2-)) in quantum dot-sensitized solar cells.
J Am Chem Soc 2011; 133: 960715.
29. Zhang Q, Uchaker E, Candelaria SL, Cao G. Nanomaterials for
energy conversion and storage. Chem Soc Rev 2013; 42:312771.

PAGE 17

30. Baskoutas S, Terzis AF. Size-dependent band gap of colloidal

quantum dots. J Appl Phys 2006; 99: 013708.

PAGE 18