Perovskite Solar cells:

Potentials, Materials & Structure

Part 1
Introduction
• Most abundant and clean form of renewable energy.
• Ease of fabrication
• Cost efficient
• Broad spectrum solar absorption
• Low non-radiative recombination loss
• Earth abundant raw material
• Increasing power conversion efficiency
• Panchromatic absorption (Absorb visible light of all colours)
The Phenomena
• Family of material with crystal structure of calcium titanate, ABX3
• Where A and B are cations and X in an anion of different dimensions of A
being larger than X
• A is a larger organic cation typically methylammonium (CH3NH3+) with rA
= 0.18 nm , ethylammonium(CH3CH2NH3+) (rA = 0.23 nm) and
formamidinium (NH2CH=NH2+) (rA is estimated in the range 0.19–0.22 nm)
• Anion X is a halogen, typically Iiodine (rX = 0.220 nm), though Br and Cl
are also increasingly being reported (rX = 0.196 nm and 0.181 nm)
• typically in a mixed halide configuration. Pb (rB = 0.119 nm) and Sn (rB =
0.110 nm), as cation B
Structures and Working Principle of
Perovskite Solar Cells
• Perovskite materials have attracted wide attention because of the
cubic lattice-nested octahedral layered structures and the unique
optical, thermal, and electromagnetic properties.

Fig: Typical perovskite lattice structure

• The metal-halogen octahedral are joined together to form a stable
three-dimensional network structure.
• The materials possess excellent photoelectric properties and high
optical absorption coefficients (up to 104 cm−1) .
• Perovskite as the light-absorbing layer can absorb solar energy
efficiently.
• The materials possess a large dielectric constant and electrons and
holes can be effectively transmitted and collected.
• Electrons and holes can be transmitted simultaneously and the
transmission distance is up to 100 nm or more and even more than
1um.
Fig: Schematic diagram of energy levels and transport process of
electrons and holes in a HTM/perovskite/TiO2 cell.
• (i) Electrons injecting into TiO2.
• (ii) Holes injecting into HTM.
• (iii) Exciton(a mobile concentration of energy in a crystal formed by an
excited electron and an associated hole) annihilation.
• (iv) Photoluminescence, or non radiative recombination.
• (v) Reverse transmission of electrons and holes.
• and recombination at the TiO2/HTM interface will also occur.
Fig: Schematic diagram and SEM section image of (a) mesoscopic architecture PSCs and (b) Planar
heterojunction structure PSCs
Mesoporous Structure
• A typical mesoporous solar cell consists of a FTO (Fluorine-doped tin
oxide) electrode, a dense electron transport layer, a mesoporous oxide
layer, a perovskite layer, a hole transport layer, and an electrode layer.
• TiO2 is the most typical mesoporous framework material.
• TiO2 plays significant functional roles, such as transporting electrons,
blocking holes, and inhibiting the recombination of the electron-hole
pairs in the FTO conductive substrate, which contributes to improving
the photoelectric conversion efficiency of the device.
• In addition to TiO2, the commonly used frame materials include
mesoscopic metal oxides, such as ZnO, Al2O3, and ZrO2.
Plane Hetero-structures
• The main difference from the mesoscopic structure is that the planar
structure removes the porous metal oxide framework.
• Higher electron mobility by using yttrium-doped TiO2.
• maximum PCE of 15.7%, and Voc of 1.03 V
Advances in Perovskite Solar Cells
• Mixed X Halide Anions: The band gap of MAPbX3 can be
controlled by adjusting the p orbit of mixed X halide anions.
• Two most stable configurations corresponding to ordered
• Structures of MAPbIBr2 and MAPbI1/2Br5/2 . These two ordered
structures provide the structural, so that the internal strain is
minimized and the architecture is most stable.
• Mixed A Site Cations: In the cubic perovskite structure, band
structure of perovskite can be adjusted within a certain range by
changing the size of the A-site ions.
• A larger or smaller cation causes the lattice to expand or contract.
• For better stability Inorganic materials such as Cs+ and Rb+ .
• organic HTM and metal electrode are completely eliminated and a
layer of carbon electrode was coated on the CsPbBr3 layer to build an
all inorganic PSC
• It can be operated in ambient environment without humidity control.
• Mixed B-Site Cations: The toxicity of Pb allows Sn to be used as an
alternative choice.
• However due to narrow band gap, the open circuit voltage of the
structure decreased.
• Self doping of Sn2+ to Sn4+ affects the stability of the Perovskite film.
• The hybrid Sn-Pb perovskite solar cells
• Modified with the C60 additive were demonstrated to have superior
stability and efficiency when exposed to the ambient Environment.
• The addition of SnCl2 in the light-absorbing layer was the most
significant for improving the stability and could not reduce the
energy-conversion efficiency
• Simultaneous Mixed A- and X-Site Ions: generally focused on the design of
multicomponent perovskites to achieve a stable, single, pure phase that can
enable the creation of stable structures with optimal transport and even
higher PCEs.
• Electron Transport Layer: Basic function is to form an electron-selective
contact with the perovskite light-absorbing layer to improve the extraction
efficiency of photo-generated electrons and to effectively prevent the hole
from migrating to the counter electrode so as to enhance the carrier’s
separation effect and to reduce the recombination.
• At present TiO2 is being used. In addition ZnO and n-type semiconductor
with higher carrier mobility is also being used.
• The n-type semiconductor also needs to be transparent to visible light,
preparation condition should be mild and band structure should match the
perovskite material.
• Hole Transport Layer: It collects and transports holes from the
perovskite light-absorbing layer to promote the separation of the
electron-hole pairs in the perovskite materials through cooperating
with the electron transport layer.
• According to the chemical composition, hole transport materials in
perovskite solar cells can be divided into two types: organic and
inorganic hole transport materials.
• Inorganic HTM show potential to replace organic ones due to high
mobility, wide band gap, and simple solvent treatment process.
Non Radiative Recombination
• Non radiative recombination is a process in phosphors and
semiconductors whereby charge carriers recombine with releasing
phonon instead of photons.
• It is an unwanted process because it lowers the light generation
efficiency and increases heat losses.