Efficient Hybrid Solar Cells Based on MesoSuperstructured Organometal Halide Perovskite

Margareta Vania Stephanie / 10213076

Group 6
Department of Physics
Institut Teknologi Bandung
Bandung, Indonesia
margavanstep@gmail.com
AbstractPerovskite is new materials of solar cell that have
highly crystalline absorber with intense visible to near-infrared
absorptivity. This material can be made at lower tempertaute and
cheaper than silicon. Concept of perovskites is binding organic
and inorganic components into a molecular composite, based on
halides that demonstrate excellent performance as light-emitting
diodes. We also replace titania nanoparticles (TiO 2) with alumina
nanoparticles (Al2O3) which electron transport through
perovskite layers was much faster that titania nanoparticles.
Using Al2O3, this perovskite give power conversion 10.9%
efficiency in a single-junction device under simulated full
sunlight. Perovskite has general structure ABX 3, where A and
B are cations and X is an anion. Degree of distortion of a
perovskite ftom ideal cubic is called tolerance factor which
perovskite structure have tolerance factor between 0.8 < t <1.0.
Applications of solar cells are photovoltaics, lasers and
photoelectrolysis.
Keywords Al2O3; Efficiency, Perovkites; TiO2; Solar Cell

I.

INTRODUCTION

Solar Energy is energy that comes from the sun. The

energy uses by solar cells that convert sunlight into electricity.
Solar cells are composed of various semiconductors.
Semiconductors are materials, which become electrically
conductive when supplied with light or heat, but which
operate as insulators at low temperatures. Nowadays, a lot of
people still refer solar cells to slilicon. Today, the best silicon
cells have efficieny about 25%. Although high efficiency,
silicon cells are high-temperature processing and costly. Solar
cell must continue to improve in efficiency and lower cost.
Perovskite is the answer for the next solar cells generation.
Perovskite first discovered by Gustav Rose in 1839 from
samples found in the Ural ountains and named after Russian
mineralogist L. A. Perovski. This upstart solar material can be
made at lower temperature and cheaper than silicon. The
ingredients of perovskite are abundant and they can be
combined easily. The thin films also have highly crystalline
structure similar to that achievd in siliscon. Although the
efficiency is low, but there are still time to develop this
material so that perovskite gets high efficiency.

II. HOW SOLAR CELLS WORK

Todays most common solar cells is made from single
juction semiconductor material. When sunlight strikes the
solar cell, it is absorbed within the semiconductor material.
This means that the photon energy of the absorbed light is
transferred to the semiconductor. Only photons whose energy
is equal to or greater than the band gap of the cell material can
free an electron. The electron flow provides the current, and
the cell's electric field causes a voltage.
In other words, the response of single-junction cells is
limited to the portion of the sun's spectrum whose energy is
above the band gap of the absorbing material, and lowerenergy photons are not used.
One way to solve this problem is using two (or more)
different cells, with more than one band gap and more than
one junction, to generate a voltage. These are called as
multijunction cells. Multijunction cells can achieve a higher
total conversion efficiency because they can convert more of
the energy spectrum of light to electricity.
In Fig. 1, a multijunction device is a stack of individual
single-junction cells in descending order of band gap (Eg).
The top cell captures the high-energy photons and passes the
rest of the photons to be absorbed by lower-band-gap cells. As
an example, the multijunction device in Fig. 1. uses a top cell
of Gallium Indium Phosphide, "a tunnel junction," to aid the
flow of electrons between the cells, and a bottom cell of
Gallium Arsenide[1].

mesosuperstructured solar cell (MSSC) as the

photogenerated electrons are not transferred to alumina
because of the difference in band edges of alumina and
perovskite active layer, which acts only as a scaffold for
carrying the photoactive layer [4]. This meso-superstructured
solar cell produce few energy losses. Although, the absorber
band gap relatively narrow (1.55 electron volts), perovskite
can generate photovoltages more than 1.1 volts.
IV. STRUCTURE OF PEROVSKITE

Fig.1. Multijunction Cells

III. HYBRID AND MESO-SUPERSTRUCTURED SOLAR

CELLS
Hybrid solar cells are material that combine organic and
inorganic semiconductors. The organic material consist of
conjugated polimers that absorb light as the donor and
transport holes. The inorganic materials are acceptor and
electron transporter in the structure. There are three main
nanoscale structures of hybrid solar cells: mesoporous
inorganic films infused with electron-donating organic,
alternatining inorganic-organic lamellar structures, and
nanowire structures[2]. For high-efficiency hybrid solar cell,
researchers have used mesoporous films. The organic absorbs
light, and transfers electrons to the inorganic semiconductor.
Inorganic then transfers the electron to the electrode.
There are several types of hybrid solar cells. One of the
best of hybrid solar cells is dye-sensitized solar cell (DSSC).
This solar cells consists of a photo-sensitized anode, an
electrolyte, and a photo-electrochemical system. Hybrid solar
cells based on dye-sensitized solar cells are formed with
inorganic materials (TiO2) and organic materials. TiO2 is the
preferred inorganic material because the material is easy to
synthesize and acts as a n-type semiconductor. Dye-sensitized
solar cells were considered as a low-cost alternative to silicon.
However, titania only absorbs a small fraction of the UV
spectrum. The efficiency also still smaller than silicon (the
best efficiency of dye-sensitized solar cell now is 12.3%)
because the efficiency of a DSSC is strongly dependent on the
charge recombination at the interface: the injected electron can
be recaptured by the dye before diffusing into the bulk of
TiO2, causing losses of efficiency.
The basic concept of the dye-sensitized solar cell has also
provided a good launching point for mutations to further
improve this performance[3]. One examples of mutation is
coating TiO2 with thin layers of Al 2O3 to enhance the
performance of dye-sensitized solar cells. This coating give
high efficiency.
Lee and his group [8] used mixedhalide form:
methylammonium lead iodide chloride (CH3NH3PbI2Cl) in
perovskite.
This
device
structure
was
called

Perovskite has general structure ABX3, where A and B

are cations and X is an anion. The A and B cations can
have a variety of charges but for X usually using Oxigen
(O). For examples, the original Perovskite mineral, CaTiO 3,
the A cation is divalent and the B cation is tetravalent. Due to
the large number of perovskite compositions possible from
combinations of cations on the lattice site, 96 compositions
were chosen. The ions occupying the A and B lattice sites are
detailed in Fig. 2.

Fig. 2. Schematic of Compositions of Perovskites Under Study.

The structure of an ideal cubic perovskite is shown in Fig.

3.,where the A cations are shown at the corners of the cube,
and the B cation in the centre with oxygen ions in the facecentred positions. Blue spheres represent the A cations, yellow
spheres represent the B cations, and red spheres represent
oxygen anions forming an octahedra.

Fig. 3. Structure of an Ideal Cubic Perovskite

Many early studies reported that the perovskites showed

mainly cubic structure, but as work on these systems
continued, the number of proposed symmetries increased. In.,
blue spheres in orthorhombic perovskite unit cell represent the
A cations, yellow spheres represent the B cations, with red sphe
resrepresenting oxygen ions. Fig. 4(b). is rhombohedral
perovskite unit cell. Blue spheres represent the A cations,
yellow spheres represent the B cations, and red spheres
represent oxygen[5].

exhibited power conversion efficiencies near 8%. Fig. 6. is the

structures of solar cell based mesoporous TiO2.

(a)

(b)

Fig. 4. Structure of Perovskite: (a) orthorhombic, (b) rhombohedral

Degree of distortion of a perovskite ftom ideal cubic is

called tolerance factor (Goldschmidt tolerance factor). It is
used to describes perovskite structure. The tolerance factor can
also be used to calculate the compatibility of an ion with a
crystal structure.

Fig. 4. Tolerance Factor Equation

Tolerance factor have value:

0.8 < t <1.0; perovskites structure

t > 1; B ion requires a smaller site

t < 0.8; the distorded perovskite structure is no longer

stable and A ion needs a smaller site

Fig. 6. Solar Cell Based Mesoporous TiO2

Al2O3 or Aluminium oxide is a chemical compound of

aluminium and oxygen and usually called alumina. Al2O3 is
an electrical insulator but has a relatively high thermal
conductivity (30 Wm1K1) for a ceramic material. Aluminium
oxide is insoluble in water. In its most commonly occurring
crystalline form, calledcorundum or -aluminium oxide, its
hardness makes it suitable for use as anabrasive and as a
component in cutting tools.
When the mesoporous n-type TiO2 is replaced with
insulating Al2O3, it will improved the power conversion
efficiency. The Al2O3 is an insulator with a wide band gap (7
to 9 eV) and purely acts as a scaffold upon which the
perovskite is coated. Electron transport through the perovskite
layer was much faster than through the n-type TiO 2. There is
also an increase in Voc (voltage open-circuit; moving from the
TiO2 to the insulating Al2O3 scaffold) of a few hundred
millivolts and a power conversion efficiency of 10.9% under
simulated full solar illumination. Fig.7. is the structure of solar
cell based esoporous Al2O3.

Fig. 5. Some Structure of Crystall and Their Tolerance Factor

From Fig. 5., GdFeO3 and SrTiO3 are perovskites (between 0.8
and 1.0), while BaNiO3 is not a perovskite (t>1)[6].
V. TIO2 VS AL2O3
TiO2 or Titanium dioxide or Titanium(IV) oxide is a white
solid inorganic substance that is thermally stable, nonflammable, poorly soluble, and not classified as hazardous
according to the United Nations (UN) Globally Harmonized
System of Classification and Labeling of Chemicals (GHS)[7].
It is sourced from ilmenite, rutile and anatase. The chemical
composition of TiO2 are 59.93% of Titanium and 40,55% of
Oxygen.
TiO2 in perovskite is an absorber and the transparent -type
component.
With
2,2,7,7-tetrakis-(N,Ndi-pmethoxyphenylamine) 9,9-spirobifluorene (spiro-OMeTAD)
as the transparent p-type hole conductor, these devices

Fig. 7 Solar Cell Based Mesoporous Al2O3

This is how TiO2 works. After light absorption, electrons

will be transferred to the TiO 2 (with subsequent electron
transport to the FTO electrode through the TiO 2) and holes
would be transferred to the spiro-OMeTAD (with subsequent
transport to the silver electrode). For Al 2O3-based cells, the
electrons must remain in the perovskite phase until they are
collected at the planar TiO 2-coated FTO electrode, and must
hence be transported throughout the film thickness in the
perovskite. Hole transfer from the photoexcited perovskite to
the spiro-OMeTAD should occur in much the same way as in
the sensitized device. Al2O3 did not act as an n-type oxide in
DSSCs.

obstacle or a trap, losing their energy in the form of waste

heat. The higher the crystal quality, the fewer berriers that
interfere the electrons journey[9].

Fig. 8. Schematic ilutrating the sharge transfer and charge transport in TiO2
solar Cell (left) and Al2O3-base solar cell.

The sensitized TiO2 solar cell (see Fig. 9.; black dashed
line) exhibited a short-circuit photocurrent (Jsc) = 17.8 mA
cm2, Voc = 0.80 V, producing an overall power conversion
efficiency of 7.6%. And for The most efficient device, Al 2O3based device (see Fig. 9.; red dashed line) exhibited Jsc = 17.8
mA cm2, Voc = 0.98 V, producing efficiency 10.9%. The third
curve (see Fig. 9.; blue dashed line) shows a device with Jsc =
15.4 mA cm2 and Voc = 1.13 V, producing efficiency 7.8%.
The general trend is that the Al2O3 cells generated open-circuit
voltages that were >200 mV higher than those generated by
the sensitized TiO2 solar cells, with comparable short-circuit
currents and slightly lower fill factors. From the solar cell
measurements on alumina-based devices, it was apparent that
the perovskite layer could function as both absorber and ntype component, transporting electronic charge out of the
device[8].

There are a lot of types solar cells, but the efficiency of

each types have differencies. An efficient solar cell must
absorb over a broad spectral range, from visible to nearinfrared (near-IR) wavelengths (350 to ~950 nm), and convert
the incident light effectively into charges. There are two solar
cells efficiency factor. First, cell temperature. As temperature
increases, the band gap of the intrinsic semiconductor shrinks.
It means that more incident energy is absorbed because a
greater percentage of the incident light has enough energy to
raise charge carriers from the valence band to the conduction
band. In Fig. 10., we see that lower temperature produce
higher voltage.

Fig. 10. I-V and P-V Characteristics of Solar Cell at the Constant
Illumination When Temperature Changes.

Second, energy conversion efficiency. The energy

conversion efficiency () of a solar cell is the percentage of
the solar energy to which the cell is exposed that is converted
intoelectrical energy. This is calculated by dividing a cell's
power output (in Watts) at its maximum power point (Pm) by
the irradiance (input light), G, in W/m2 and the surface area of
the solar cell (Ac in m2).

Fig. 10. Solar Cells Efficiency Equation.

Fig. 9. Current density-voltage characteristics of TiO2 (black dashed line),

Al2O3 (red dashed line) and other material (blue dashed line).

VI. EFFICIENCY OF PEROVSKITE

Solar cell efficiency is the ratio of the electrical output of a
solar cell to the incident energy in the form of sunlight. Solar
cells cant convert 100% of the suns light energy because of
the exitable electron. When a solar cell is in the dark, electrons
in the material stay bound to their respective atoms; no
electricity flows. But when sunlight strikes a cell, it can
release some of the electrons. The energy from sunlight, can
make the excitated electrons move through the crystal lattice
of the cell until they either exit one end of the cellcarried
away by an electrode as useful currentor run into an

In order to increase the energy conversion efficiency of the

solar cell by reducing the reflection of incident light, two
methods are widely used. One is reduction of the reflection of
incident light with an antireflection coating, and the other
is optical confinements of incident light with textured
surfaces. The change of the spectral irradiance also influences
the solar power generation. The solar spectrum can be
approximated by a black body of 5900 K which results in a
very broad spectrum ranging from the ultraviolet to the near
infrared. On the other hand, a semiconductor can only convert
photons with the energy of the band gap with good efficiency.
Photons with lower energy are not absorbed and those with
higher energy are reduced to gap energy by thermalization of
the photo generated carriers[10].
Every year, topic research of Perovskite grows every year
(see Fig. 11). Researcher are interested to develop this new

solar cells because there are still big opportunity to obtain high
efficiency.

(PV) is a method of converting solar energy into direct current

electricity. A photovoltaic system employs solar panels
composed of a number of solar cells to supply usable solar
power. Power generation from solar PV has long been seen as
a clean and sustainable energy technology which draws upon
renewable energy source the sun. The direct conversion of
sunlight to electricity occurs without any moving parts or
environmental emissions during operation[13].

Fig.11. Topic Seach of Perovskite Cell per Year[11]

In 2009, a group at Toin University modify a lead halide

perovskite into a solar cell. This film generated electrons when
it absorbed sunlight but not very well. The first tiny cells were
only 3.8 percent efficient, and they were highly unstable,
deteriorating within hours. In 2012, Lee and the group [8]
replaced TiO2 with Al2O3, produce efficiency 10.9%. The
recent publications, there are some researchs that innovate the
perovskites and produce until 20% efficiency. The new paper
produce high-performance photovoltaic perovskite layers
fabicated through intramolecuar exchange. They fabricated
formamidinium lead iodide (FAPbI3) and give power
conversion greater than 20%[12].
From the story above, we see that perovskite research
grows very rapidly. In Fig. 12., we se that perovskites research
(violet dashed line) rise significanly than the other material.
Silicon (pink dashed line) need amost 40 years to achieved
25% efficiency. Perovskite just need 5 years to achieved 20%
efficiency.

Fig.13. Concept of Photovoltaics System[14]

From Fig. 13., a conducting wire connects the p-type

silicon to an external load such as a light or battery, and then
back to the n-type silicon, forming a complete circuit. As the
free electrons are pushed into the n-type silicon they repel
each other because they are of like charge. The wire provides a
path for the electrons to move away from each other. This
flow of electrons is an electric current that can power a load,
such as a calculator or other device, as it travels through the
circuit from the n-type to the p-type. It is this flow of electrons
that produces electrical current.

Fig.14. PV Array Components [14]

A PV System typically consists of three basic components

that are PV cells, modules, and arrays (see Fig. 14.).
Electricity is generated by PV cells, the smallest unit of a PV
system. Then, PV cells are wired together to form modules
which are usually a sealed, or encapsulated, unit of convenient
size for handling. Finally, groups of panels make up an array.
Fig.12. Best Reseach-Cell Efficiencies of Some Solar Cell Material [11]

VII. APPLICATION OF PEROVSKITES

There are three application of perovskites that are
photovoltaics, laser and photoelectrolysis. First, photovoltaics

produced an optically driven laser which proves perovskite

cells can re-emit up to 70%
optical-to-optical lasing
efficiency of absorbed light[17].

Fig.15. Worldwide growth of photovoltaics [15]

Solar photovoltaics is growing rapidly and worldwide

installed capacity reached at least 177 gigawatts (GW) by the
end of 2014. The total power output of the worlds PV
capacity in a calendar year is now beyond 200 billion kWh of
electricity. More than 100 countries use solar PV.
Photovoltaics is now, after hydro and wind power, the third
most important renewable energy source in terms of globally
installed capacity.
Second, perovskites can be used as laser. The fundamental
experiment is guided by Deren and Mahiou in paper
LaAlO3 crystal doped with Er3+. LaAlO3 is notable material
interface because it exhibits properties not found in its
constituent materials. LaAlO 3 single crystal provides a good
lattice match to many materials with perovskite structure. It
can be used as substrate for semicondutors, magnetic and
ferromagnetic thin films. Erbium (with atomic number 68) is
used for long-distance optical communication systems
(emission at about 1550 nm ).

Fig.17. Perovskites as Laser[17]

Third, perovskites can be used as photoelectrolysis. This

system is highly efficient and low-cost water-splitting cell
combining perovskite solar cell and NiFe catalyst. NiFe
exhibits high activity toward both the oxygen and hydrogen
evolution. Splitting water requires an applied voltage of at
least 1.23 V to provide thermodynamic driving force. This
system also using perovskite solar cells based on CH 3NH3PbI3
(methylammonium lead iodide). Solar-to-electric power
conversion gives efficiency (PCE) of 17.3% while solar-tohydrogen give efficiency = 12.3%.

Fig.18. Water Splitting Device[18]

Fig.16. Infrared Emission Spectrum of LaAlO3[16].

From the experiment, researchers found a result in Fig.

16. That LaAlO3 can give emission spectrum which exited at
488 nm by an Argon Laser with T = 297 K. So, they conclude
that perovskites should be use as laser.
Also in 2008 researchers demonstrated that perovskite can
generate laser light. LaAlO3 doped with neodymium gave
laser emission at 1080 nm. In 2014, it was shown that
methylammonium lead iodide perovskite (CH3NH3PbI3-xClx)
cells fashioned into optically pumped vertical-cavity surfaceemitting lasers (VCSELs) convert visible pump light to nearIR laser light. By putting a thin layer of the lead halide
perovskite between two mirrors (see Fig. 17.), the team

In Fig. 18., perovskites solar cells were placed side by

side and connected with wires to the immersed catalyst
elecyrodes and simulated solar irradiation provided the energy
to split water. At the negatively charged cathode, a reduction
reaction takes place, with electrons (e) from the cathode
being given to hydrogen cations to form hydrogen gas:
Reduction at cathode: 2 H+(aq) + 2e H2(g)
At the positively charged anode, an oxidation reaction occurs,
generating oxygen gas and giving electrons to the anode to
complete the circuit:
Oxidation at anode: 2 H2O(l) O2(g) + 4 H+(aq) + 4e
Then, the reactin total is:
Overall reaction: 2 H2O(l) 2 H2(g) + O2(g)
IX.
1.
2.

CONCLUTIONS

Perovskite is upstart solar cells material that can be

made at lower temperatures and cheaper than silicon
solar cell.
Hybrid solar cell combine organic and inorganic
material.

3.
4.
5.
6.
7.

Meso-superstructured solar cell produce few energy

losses.
General structure of perovskite material is ABX 3
where A and B are cations and X is an anion.
Factors of Solar Cell Efficiency are temperature and
energy conversion efficiency.
Efficiency of AL2O3 is higher than TiO2 which
AL2O3 solar cell efficiency is 10.9% and TiO2 solar
cell is 7.6%.
Application of perovskite is for photovoltaic, laser,
and photoelectrolysis.
REFERENCES

[1]
[2]

[3]
[4]

[5]

[6]

[7]

Knier, Gil. How do Photovoltaics Work? Ritrieved from

http://science.nasa.gov. [9 November 2015]
Vats, A., Shende, R., Swiatkiewicz, J. & Jan Puszynski. Chapter 2:
Renewables: Photovoltaics, Wind & Geothermal. Mesoporous TiO 2
Thin-Film for Dye-Sensitized Solar Cell (DSSC) Application. Clean
Technology 2008. Technical Proceedings of the 2008 Clean Technology
Conference and Trade Show. pp. 113-116.
Nerris, D. J., & Eray S. A. Material Science: Getting Moore from Soalr
Cells. Science, vol. 338. pp. 625-626.
Ahmed, M. I., Habib, A., & Syed Saad Javaid. Review Article:
Perovskite Solar Cells: Potentials, Challenges, and Opportunities.
International Journal of Photoenergy, 2015. doi:10.1155/2015/592308.
Chapter
3:
Perovskite
Perferct
Lattice. Retrieved
from
http://abulafia.mt.ic.ac.uk/publications/theses/levy/Chapter3.pdf
[9
November 2015]
Important Crystal Structure: Perovskite Structre. Retrieved from
http://n.ethz.ch/~nielssi/download/4.%20Semester/AC
%20II/Unterlagen/perovskites.pdf [9 November 2015].
About Titanium Dioxide. Titanium Dioxide Stewardship Council.
Retrieved
from:
http://www.cefic.org/Documents/Industry

[8]

[9]
[10]

[11]

[12]

[13]
[14]

[15]

[16]
[17]

[18]

%20sectors/TDMA/About-TiO2-full-version-July-2013.pdf
[9
November 2015].
Lee, M.M., Teuscher, J., Miyasaka, T., Murakami, T. N., & Henry J.
Snaith. Efficient Hybrid Solar Cells Based on Meso-Superstructured
Organometal Halide Perovskites. Science, vol. 338. pp. 643-646.
Sivaram, V., Stranks, S. D., & Henry J. Snaith. Outshining Silicon.
Scientific American. pp.56
Dincer,F. & Mehmet Emin Meral. Critical Factors that Affecting
Efficiency of Solar Cells. Smart Grid and Renewable Energy, 2010. pp.
47-50.doi:10.4236/sgre.2010.1100.
Feng, Wenchun. Perovskite Solar Cells. Department of Chemistry and
Chemical Biology. University of Michigan. Retrieved from
http://www.slideshare.net/WenchunFeng/perovskite-solarcellswenchunfeng.
Yang, W. S., Noh, J. H., Jeon, N. J., et al. High-Performance
Photovoltaic Perovskite Layers Fabicated Through Intramolecular
Exchange. Science, vol. 348. pp. 1234.
Pearce, Joshua (2002). "Photovoltaics A Path to Sustainable Futures".
Futures 34 (7): 663674. doi:10.1016/S0016-3287(02)00008-3.
Energy from the Sun Workshop: Introduction to Photovoltaics.
Retrieved
from:
http://cse.ssl.berkeley.edu/energy/Resources/Introduction%20to
%20Photovoltaics%20Powerpoint.pptx [5 Deccember 2015]
Photovoltaics.
Retrieved
from:
https://en.wikipedia.org/wiki/Photovoltaics#cite_note-2 [5 Deccember
2015]
Deren, P. J. and R. Mahiou. Spectroscopic Characterisation of LaAlO 3
Crystal Doped with Er3+ Ions. Optical Materials 29 (2007) 766-772.
Study: Perovskite Solar Cells Can Double as Lasers. Retrieved from:
http://www.rdmag.com/news/2014/03/study-perovskite-solar-cells-candouble-lasers
Jingshan Luo; et al. 2014. "Water photolysis at 12.3% efficiency via
perovskite photovoltaics and Earth-abundant catalysts". Science 345
(6204): 15931596. doi:10.1126/science.1258307