1
Fundamental Understanding
of Solar Cells
Kevin P. Musselman, Kianoosh Poorkazem
DE PARTMENT OF MECHANICAL AND MECHATRONICS ENGINEERING, UNIVERSITY O F
WATERLOO , WATERLOO, ON, CANADA
1. Operation of a Photovoltaic Solar Cell
1.1 Photovoltaic Fundamentals
In photovoltaic energy conversion, an incident photon imparts energy to an electron
in an absorbing material, promoting the electron to an excited state. Commonly this
corresponds to an electron being excited from the valence band to the conduction
band in a semiconductor. In a photovoltaic solar cell, some built-in asymmetry is pre-
sent to remove the excited electrons (and the energy associated with them) before
they can relax to their lower-energy states. Typically, this asymmetry is provided by
an interface between an electron-conducting (n-type) material and a hole-conducting
(p-type) material, as in the p-n junction illustrated in Fig. 1. The asymmetric junction
separates the excited electrons and holes (vacant electron states) and collects them at
opposite electrodes of the device, producing a potential that can power an external
circuit.
The equivalent circuit for a solar cell is shown in Fig. 2. The short-circuit current den-
sity Jsc is the current resulting from light absorption when the cell is measured in a short-
circuit configuration, such that there is no potential difference V across it. The direction of
Jsc through the cell is shown in Figs. 1 and 2. The asymmetric p-n junction is represented
by a diode circuit element in Fig. 2. The formation of a potential difference across the cell
results in a dark current density Jdark in the diode, as shown in Fig. 2, that opposes the
short-circuit current density Jsc created by light absorption. Parasitic resistances that exist
in the solar cell and reduce the achievable power output are also shown in Fig. 2. The series
resistance Rseries corresponds to the resistance to current in the junction materials and
current-collecting electrodes. It results in a parasitic voltage drop in the solar cell, which
reduces the external potential V that can be produced. Any disruption in the asymmetry of
the cell results in leakage current through the cell, which corresponds to a shunt resistance
Rshunt, as shown in Fig. 2. For efficient cell operation, a low Rseries and high Rshunt are
desirable.
Advanced Micro- and Nanomaterials for Photovoltaics. https://doi.org/10.1016/B978-0-12-814501-2.00001-3 1
© 2019 Elsevier Inc. All rights reserved.
2 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
FIG. 1 Basic operation of a photovoltaic solar cell: a photon is absorbed, exciting an electron to a higher energy state.
A built-in asymmetry separates the electron and hole, resulting in the generation of current and voltage.
Rseries
Rshunt V
Jsc Jdark
–
FIG. 2 Equivalent circuit for a photovoltaic solar cell.
Following from this equivalent circuit, the net current density J and voltage V produced
by the cell can be related to the given parameters:
qðV + JAR Þ
series V + JARseries
J ¼ Jsc J0 e mkT 1 (1)
ARshunt
In this equation, J0 is a constant describing the dark current density, q is the electron
charge, A is the area of the solar cell, m is the ideality factor describing the dark current’s
dependence on applied bias, k is the Boltzmann constant, and T is the temperature.
1.2 The Silicon Photovoltaic Solar Cell
The solar cell described in Section 1 is the basic building block of a photovoltaic system.
When illuminated by the sun, the voltage produced by a typical cell, such as the silicon
solar cell discussed in this section, is around 1 V or less. This voltage is insufficient for most
applications, so solar cells are typically connected together in series to form a photovoltaic
module, a schematic of which is shown in Fig. 3A and is easily recognizable from roof-top
and utility-scale photovoltaic installations.
Chapter 1 • Fundamental Understanding of Solar Cells 3
FIG. 3 Schematics of (A) a photovoltaic module and (B) a cross-section of a traditional silicon solar cell.
The majority of photovoltaic modules currently in use consist of silicon solar cells.
A traditional silicon solar cell is fabricated from a p-type silicon wafer a few hundred
micrometers thick and approximately 100 cm2 in area. The wafer is lightly doped
(e.g., approximately 1016 cm3) and forms what is known as the “base” of the cell. It
may be multicrystalline silicon or single-crystal silicon. An n-type layer is produced
on the surface of the wafer using dopant diffusion to create the desired p-n junction.
The n-type layer, known as the “emitter,” is more heavily doped (e.g., approximately
1019 cm3) and much thinner than the p-type base. A schematic cross-section of a sil-
icon solar cell is shown in Fig. 3B. Prior to formation of the n-type emitter layer, the sil-
icon wafer is typically texturized via chemical etching to reduce the reflection of light
from its surface. Following the formation of the n-type layer, antireflection coatings
can be added to the surface to further enhance light absorption. These coatings can con-
sist of SiNx or TiO2, and in addition to reducing reflections, can provide some passivation
to prevent charges from getting trapped at the surface. The rear surface is more heavily
doped to create a back surface field that limits surface recombination. Metal contacts are
then applied using a printing technique, such as screen-printing of aluminum or silver.
A grid-like metal pattern is printed on the front of the cell, to limit the amount of light
blocked, whereas the metal contact on the rear side of the cell can be continuous, as
shown in Fig. 3B.
Many variations of this silicon cell architecture have been developed to improve the
performance. These include, among others, passivated emitter cells, which include a
dedicated passivation layer on the front surface; passivated emitter and rear cells
(PERC cells), which employ a dielectric passivation layer on their rear surface to reflect
unabsorbed light back into the cell; and heterojunction with intrinsic thin layer cells
(HIT cells), which sandwich the crystalline silicon between thin amorphous silicon
layers.
Silicon solar cells are prone to mechanical damage and corrosion, so the manufactur-
ing of modules includes encapsulation steps to provide suitable protection. The series-
connected cells can be encapsulated in a transparent polymer, such as ethylene vinyl
acetate (EVA), and then mounted on a sheet of glass, which acts as the top, transparent
4 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
surface of the module. An additional polymer layer, such as a sheet of polyvinyl fluoride,
can then be added to provide a further barrier to water and gases on the underside of the
module.
1.3 Measures of Photovoltaic Performance
Power is generated by a solar cell when it operates in the fourth quadrant of a current
density-voltage (J-V) graph, where voltage is positive and current negative. The power
conversion efficiency (PCE) is the most fundamental measure of solar cell performance.
It is defined as the ratio of the electric power delivered to the external circuit to the solar
power incident on the cell:
Pout FF Jsc Voc
PCE ¼ ¼ (2)
Pincident light intensity
The short-circuit current density, open-circuit voltage, and fill factor of the cell are
represented by Jsc, Voc, and FF, respectively. The open-circuit voltage Voc is the cell voltage
measured in an open-circuit configuration, such that there is zero net current through the
cell. The fill factor FF is defined as
ðJ V Þmax
FF ¼ (3)
ðJsc Voc Þ
It is the power produced at the maximum power point on the J-V curve divided by the
product of Voc and Jsc. It can be thought of as a measure of how rectangular the J-V char-
acteristic is in the fourth quadrant.
Another measure of photovoltaic performance that is often reported is the quantum
efficiency. The external quantum efficiency EQE is the ratio of electrons collected by
the solar cell to the number of incident photons at a particular energy. Ideally the EQE
is a step-function at the band edge of the light-absorbing material. The EQE at a particular
wavelength λ depends on the proportion of light that is reflected from the front surface
R(λ), the percentage of non-reflected light that is absorbed a(λ), and the efficiency with
which photogenerated electron-hole pairs are collected from the cell ηCE(λ), according to
EQE ðλÞ ¼ ð1 RðλÞÞaðλÞηCE ðλÞ (4)
If the EQE is known, the expected short-circuit current density can be calculated as
Z ∞
Jsc ¼ q EQE ðλÞϕðλÞdλ (5)
0
where ϕ(λ) is the solar photon flux. The internal quantum efficiency IQE accounts for
reflection and parasitic absorption losses. It gives the ratio of electrons collected by the
solar cell to the number of photons absorbed by the active layer, again as a function of
energy (or wavelength). The distinction between EQE and IQE is important when consid-
ering whether losses in a cell are due to optical absorption properties of the device stack,
or due to the photoconversion properties of the absorbing materials.
Chapter 1 • Fundamental Understanding of Solar Cells 5
The National Renewable Energy Laboratory (NREL) maintains a record of the highest
certified values of power conversion efficiency for different photovoltaic technologies, as
shown in Fig. 4. These PCEs are for research cells and are therefore higher than what is
obtained in commercial cells and modules, but the chart nonetheless provides an excel-
lent overview of the progress made with the various technologies.
The PCE record for a crystalline silicon cell is 25.8% in Fig. 4 and 26.6% for a HIT cells.
Fig. 4 also shows PCE records for a number of other photovoltaic technologies, many of
which will be addressed in the following sections and chapters. There are a number of rea-
sons the PCE of solar cells is not unity. These will be discussed in the next section.
2. Limitations in Photovoltaic Energy Conversion
2.1 Single-Junction Maximum Theoretical PCE
The possible PCE of the ideal, two-band, single-junction solar cell, such as that shown in
Fig. 1, depends primarily on the incident light spectrum and the band gap Eg of the
absorber. For a fixed solar spectrum, the theoretical efficiency therefore depends almost
exclusively on the band gap. This dependency is explained in Fig. 5. Photons with energies
Ephoton less than the band gap of the absorber are transmitted through the semiconductor
without being absorbed, such that their energy is lost. Photons with energies Ephoton larger
than the band gap are absorbed and excite electrons to higher-lying energy states, but
these electrons rapidly thermalize to the band edge by interacting with phonons, reducing
their electrical potential energy. Therefore, small and large band gaps result in low PCEs.
For a large Eg, few photons are absorbed to produce electrical power. For a small Eg, many
photons are absorbed, but the excited electrons lose most of their electrical potential
energy (the voltage that the cell can produce is always less than Eg). This trade-off between
current and voltage results in a maximum PCE at an intermediate band gap. For single-
junction solar cells under standard global air mass 1.5 (AM1.5G) illumination, the maxi-
mum efficiency is around 33% at a band gap near 1.3 eV for unconcentrated solar illumi-
nation [1, 2].
2.2 Strategies to Exceed the Single-Junction Limit
Several approaches have and continue to be developed to achieve PCEs beyond the single-
junction limit. Recognition that some of the losses illustrated in Fig. 5 can be avoided if
photons of different energies can be absorbed in cells with different band gaps has led
to the development of tandem (also known as multijunction) solar cells. Tandem cells
place an absorber with a large Eg on top of an absorber with a smaller Eg. The light first
passes through the absorber with the large Eg, which filters out most of the high-energy
photons, then through the absorber with the smaller Eg, where photons with smaller ener-
gies are absorbed. By matching photon energies and band gaps, the thermalization losses
shown in Fig. 5 can be minimized, while still absorbing many of the photons. This tandem
6
ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
FIG. 4 Highest confirmed power conversion efficiencies for photovoltaic cells, from 1976 to the present, for a range of photovoltaic technologies. This plot is
courtesy of the National Renewable Energy Laboratory, Golden, Colorado.
Chapter 1 • Fundamental Understanding of Solar Cells 7
FIG. 5 Fundamental losses in a single-junction solar cell: low energy photons are not absorbed and electrons excited
by high-energy photons lose energy via thermalization.
concept is shown in Fig. 6A and B in four-terminal and two-terminal designs, respectively.
The four-terminal design requires independent electrical connections for each of the two
cells, which can be challenging in practice, whereas the two-terminal design connects the
cells in series, avoiding the need for additional connections. However, the two-terminal
design requires that the currents from each cell be matched, which can also be challenging
in practice, especially in conditions of variable illumination. For the four-terminal design,
a maximum theoretical PCE of 55% is expected with band gaps of 1.65 and 0.75 eV under
full solar concentration [2]. The maximum theoretical efficiency is slightly less for two-
terminal designs, due to the current-matching requirement. Some of the materials com-
monly employed in tandems cells include GaAs, InGaP, Si, and now organometal halide
perovskites [3]. In Fig. 4, a PCE of 32.8% is reported for a two-junction tandem cell based
on GaInP and GaAs in a two-terminal design under un-concentrated illumination, and
35.5% is reported for a two-junction tandem cell based on GaInAsP and GaInAs in a
two-terminal design under concentrated illumination. Adding more band gaps can fur-
ther increase the PCE. In the limit of an infinite number of band gaps, the maximum the-
oretical efficiency reaches 69% under one sun illumination (and 86% under full
concentration). It is seen in Fig. 4 that PCEs of 44.4% and 46.0% have been achieved
for two-terminal tandems with three and four junctions, respectively, under concentrated
illumination.
Tandem cells attempt to avoid the thermalization losses illustrated in Fig. 5 by employing
several absorbers with different band gaps. Another approach is to try and harness some of
the excess kinetic energy of these excited electrons before they relax (thermalize). This can
be done if the electron-phonon interactions are slowed down (or the carrier collection sped
up, or both), so that the excited electrons can be collected while still “hot.” This process is
illustrated in Fig. 6C and would result in an increase in the cell voltage. The theoretical
maximum PCE for a hot carrier solar cell is approximately 85% under full concentration
and 65% under one sun illumination [2]. The band gaps that would provide these
maximum efficiencies are a few tenths of an eV and approximately 0.25 eV, respectively.
8 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
FIG. 6 Strategies to exceed the single-junction photovoltaic efficiency limit: (A) four-terminal and (B) two-terminal
tandem cell designs, (C) hot carrier extraction and impact ionization, (D) photon upconversion, and (E) photon
downconversion.
Hot carrier cells allow the band gap to be reduced to increase the number of photons
absorbed, without the negative effect of increased thermalization losses. In practice, ther-
malization can be slowed down in quantum well and quantum dot structures, where
electron-phonon interactions are inhibited, and devices with small dimensions can enable
Chapter 1 • Fundamental Understanding of Solar Cells 9
rapid carrier collection. An additional requirement for hot carrier cells is specially designed
contacts that are energy selective (i.e., will only accept carriers within a narrow energy
range), in order to minimize heat production of the high kinetic energy carriers in the
contacts.
Alternatively, the excess energy of the hot carriers could be used to create more carriers.
This process, known as impact ionization, Auger generation, or multiple pair generation, is
illustrated in Fig. 6C and would result in an increase in the cell current. The energetic elec-
tron collides with the lattice and gives up its kinetic energy to excite another electron
across the band gap. This enables a theoretical IQE of 200% for high-energy photons.
For 1 sun illumination, the theoretical maximum PCE for an impact ionization cell is
55% at a band gap of approximately 1 eV. Under full concentration, the theoretical behav-
ior of impact ionization cells is similar to the hot carrier cells, reaching a maximum PCE of
85% for very small values of Eg [2].
Another approach to improve the cell efficiency is to control the photon energies to
better match the band gap of the absorber. This can be achieved using photon con-
verters. Two low-energy photons (that would otherwise not be absorbed by the cell)
can be combined to produce a high-energy photon that can be absorbed. This process
is known as upconversion and is illustrated in Fig. 6D. Alternatively, one high-energy
photon (that would otherwise create a hot carrier prone to thermalization losses) can
be split to produce two photons that can still be absorbed by the cell but have smaller
energies and smaller associated thermalization losses. This process is known as down-
conversion and is illustrated in Fig. 6E. In practice, photon converters can be added
as thin films to the solar cell. Inorganic Yb+3 and Er+3 have been used to dope a number
of materials to obtain upconversion [4]. Since the Eg of organic molecules is tunable,
organic upconversion systems, such as those based on triplet-triplet annihilation, pro-
vide flexibility (compared with inorganics) in the use of different-Eg active layers
[5, 6]. Materials known to demonstrate downconversion include Gd3+, Eu3+, and Er3+
coupled in the LiGdF4 host lattice, (Y,Yb)PO4:Tb3+, CaAl2O4:Yb3+, GdAl3(BO3)4:RE3+,
Yb3+(RE ¼ Pr, Tb, Tm), YbxGd1 xAl3(BO3)4:Tb3+, YVO4:Yb3+, Er3+–Yb3+:Cs3Y2Br9, ZnO:
Eu3+, LaVO4:Dy3+, GdVO4:Dy3+, and YF3:Pr3+ [4, 7].
Finally, singlet fission in conjugated organic molecules has also received attention as a
possible route to exceed the single-junction limit. Bound electron-hole pairs in organic
semiconductors, known as “excitons,” can occupy singlet (spin ¼ 0) or triplet (spin ¼ 1)
states. In some organic semiconductors, when a photon is absorbed and creates a singlet
exciton, the exciton can be rapidly converted into two lower-energy triplet excitons. The
result is two electrons from a single photon. Studied singlet fission materials include pen-
tacene and tetracene, which can be combined with appropriate acceptor molecules or
coated onto other absorbers such as layers of inorganic quantum dots and silicon, result-
ing in EQEs >100% [8–11]. In these devices, the other absorber can absorb low-energy
photons, whereas high-energy photons can be absorbed by the singlet fission sensitizer
to produce two electrons and avoid thermalization losses in a manner similar to the
impact ionization process shown in Fig. 6C.
10 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
2.3 Other Losses in Solar Cells
The absorption spectrum of a solar cell dictates, to a large degree, the loss of energy in the
cell. Any light that is transmitted or reflected is incident power lost. Once energy is
absorbed as excited electrons, energy can be lost by thermalization of the carriers to
the band edges, as discussed in Section 2.1, and also via the recombination of excited elec-
trons and holes. In relation to Fig. 2 and Eq. (1), recombination reduces the photocurrent
and voltage by increasing the dark current J0. Recombined carriers do not generate elec-
trical power, and hence lower the PCE of the cell.
Some mechanisms of recombination are unavoidable. Radiative recombination (spon-
taneous or optically stimulated) is always expected; however, it is balanced somewhat by
reabsorption of the emitted light. Likewise, Auger recombination is unavoidable and
expected to be significant in materials with small bandgaps and high carrier concentra-
tions. The Auger process is similar to impact ionization discussed in the last section; how-
ever, in this case, two similar carriers interact, causing one to decay across the band gap
and transfer its kinetic energy to the other (rather than exciting an additional carrier across
the band gap, as in impact ionization).
Nonradiative recombination arises from material imperfections. In nonradiative,
Shockley Read Hall recombination, relaxation of a photogenerated electron occurs via
a localized trap state. When an electron is captured by a trap state in the band gap, it
may subsequently be released by thermal activation (“detrapping”). However, if the trap
state also captures a hole before the electron is released, recombination occurs. Trap states
located deep within the band gap have a higher probability of capturing both electrons
and holes, and are therefore commonly referred to as recombination centers. Recombina-
tion can occur at defects within the grains of the active materials, at impurities, and at
interfaces, including heterojunctions and grain boundaries. As the density of recombina-
tion centers increases, the lifetimes of electrons in the conduction band and holes in the
valence band decrease (carriers are captured more quickly by the deep trap states). The
charge carrier transport length and lifetime are thus critical parameters in solar cells.
The carrier transport length should be longer than the thickness of the material needed
for complete light absorption, to prevent recombination en route to the collection elec-
trodes. Charge transport lengths are generally highest in uniform, crystalline materials
free from defects, impurities, and grain boundaries.
3. Emerging Photovoltaic Materials and Photovoltaic
Solar Cells
Considerable effort has been expended in recent years to develop new photovoltaic mate-
rials and architectures. Photovoltaic silicon has a diamond cubic crystal structure, but a
variety of different silicon phases and composites are known to exist and continue to be
discovered, such as clathrates and nanostructures [12]. Nano-engineered forms of silicon
can be tailored to improve the efficiency of solar energy conversion. Biomimetic
Chapter 1 • Fundamental Understanding of Solar Cells 11
photovoltaic materials have also received considerable attention, such as large protein
complexes similar to those involved in photosynthesis [13]. Most recent research on
emerging photovoltaics, however, has centered on four classes of devices: dye-sensitized
solar cells (DSSCs), organic photovoltaics (OPV), colloidal quantum dot solar cells
(CQDSCs), and perovskite solar cells (PSCs).
3.1 Dye-Sensitized Solar Cells
Liquid-electrolyte dye-sensitized solar cells (DSSCs) were introduced by Gratzel and
O’Regan in 1991 [14]. A transparent conducting electrode (TCE), typically fluorine-doped
tin(IV)-oxide (FTO) on glass, is coated with a mesoporous layer of anatase titanium(IV)
oxide (TiO2), as illustrated schematically in Fig. 7A. The mesoporous layer is sintered to
produce a network of connected nanoparticles (approximately 20 nm in diameter) with
high porosity (typically 50%–65%). The mesoporous film is coated with a monolayer of
photosensitive dye, which acts as the light absorber. For 15–20 nm particles, this
FIG. 7 Device architectures of (A) dye-sensitized solar cells, (B) bulk-heterojunction solar cells, (C) colloidal quantum
dot solar cells, and (D) perovskite solar cells.
12 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
mesoporous structure delivers a 100-fold enhancement in surface area per micron thick-
ness, as compared with a flat film [15]. A surface area approximately 1000 times greater
than the planar area ensures efficient solar harvesting, such that mesoporous film thick-
nesses are typically around 10 μm. Traditionally the mesoporous film is filled with an
iodide/triiodide-based electrolyte and capped with a platinum counter electrode. After
light-absorption by the dye, electron transfer takes place from the dye’s excited state into
the conduction band of the electron-transport material (ETM; i.e., TiO2), and the elec-
trons reach the TCE electrode via diffusion through the disordered nanoparticle struc-
ture. The iodide redox couple regenerates the oxidized dye molecules, with the
positive charge being transported through the electrolyte to the counter electrode. These
cells have demonstrated certified power conversion efficiencies up to 11.9% [16]. An
advantage of DSSCs is the variety of suitable dyes that can be employed, covering a wide
range of the solar spectrum. Liquid-electrolyte DSSCs are a relatively mature technology
and are now commercially available from several suppliers. Recent research directions in
DSSCs have included, but are not limited to, improving light harvesting through
co-sensitization, light scattering, and increasing the electrode transparency; surface
engineering through hydrogenation, protonation, and plasma treatments; novel DSSC
structures including p-type DSSCs and tandem devices; stability improvements through
the replacement of the liquid electrolyte and Pt catalyst; and cost reductions through the
use of natural dyes and the replacement of FTO and Pt with graphene. More information
about current research trends can be found in recent review articles, such as the one
from Gong et al. [17].
3.2 Organic Photovoltaics
Organic photovoltaic devices are composed of electron-transporting and hole-
transporting organic semiconductors. These materials have the potential to be cheaply
produced in large volumes, and cells can be made flexible and lightweight for a variety
of applications. Fullerene derivatives such as PCBM ([6,6]-phenyl-C61-butyric acid
methyl ester), which are small conjugated molecules, have typically been employed as
the electron transporter. Copolymers of polyfluorene, and poly(phenylenevinylene) and
poly(thiophene) backbones such as P3HT (poly(3-hexylthiophene)), have generally been
used as the hole-transporting materials. Unlike inorganic semiconductors where photo-
excitation generally results in the production of free carriers, bound states of excited elec-
trons and holes, “excitons,” are produced in organic semiconductors (with binding energy
in the order of hundreds of meV [18–21]). Bound by Coulomb attraction, the excitons are
strongly localized to individual polymer chains or molecules. Following photon absorp-
tion, excitons diffuse to the interface between the electron-transporting and hole-
transporting semiconductors. An offset in the energy levels of the two materials at the
interface facilitates dissociation of the exciton into a free electron and hole. Following dis-
sociation, the electrons and holes are transported through their respective organic layers
to either an ETM or a hole-transport material (HTM) interface, and then to the electrodes.
Chapter 1 • Fundamental Understanding of Solar Cells 13
Charge transport in these materials results from carrier hopping between the molecules or
chains, such that mobilities are lower than in inorganic equivalents. The exciton diffusion
length, in particular, is typically reported to be on the order of 10 nm [22]. The efficiency of
organic solar cells is therefore very sensitive to the morphology of the materials on the
nanoscale. Interfacial distances need to be suitably small so that photogenerated excitons
can be dissociated. Continuous pathways are also necessary in the individual phases to
allow transport of the carriers to the electrodes. The active layer must also be suitably thick
to absorb most of the incident light. These criteria are simultaneously satisfied by produc-
ing bulk heterojunctions (BHJs), where two organic semiconductors are blended in a com-
mon solvent to form an interpenetrating network of electron and hole-transporting
materials, as illustrated in Fig. 7B. Bulk heterojunctions are typically synthesized by
spin-coating the blended solution onto a conducting glass substrate with a thin
electron-blocking layer (hole transport layer).
Many groups have studied how processing conditions and subsequent treatments
influence the performance of bulk heterojunction solar cells. Optimization of these
parameters has resulted in a certified PCE of 11.5% for cells with an architecture of
ITO/ZnO/polymer:PC71BM/V2O5/Al, with the polymer poly[(5,6-difluoro-2,1,3-ben-
000 0 0 00 00 000 000
zothiadiazol-4,7-diyl)-alt-(3,3 -di(2-nonyltridecyl)-2,2 ;5 ,2 ;5 ,2 -quaterthiophen-5,5 -
diyl)] (PffBT4T-C9C13) [23]. Here ITO refers to a thin indium tin oxide layer.
Organic photovoltaics are widely observed to degrade over time, and research efforts
are ongoing to improve their lifetime to a timeframe suitable for commercial applications.
Improvements in encapsulation and increased glass transition temperatures for the
organic materials, among other possible improvements, have been identified and are
summarized in a review by McGehee et al. [24].
3.3 Colloidal Quantum Dot Solar Cells
Semiconducting quantum dots offer important advantages over conventional bulk mate-
rials such as solution-processability, low-temperature fabrication, and quantum size-
effect tunability of their band gap, which allows their absorption properties to be opti-
mized for photovoltaic applications. The most effective solar cell architecture employing
quantum dots has been the colloidal quantum dot solar cell (CQDSC), which is shown
schematically in Fig. 7C. The CQDSC is typically based on a heterojunction between an
n-type material, such as TiO2 or ZnO, and a layer of p-type quantum dots, such as those
based on lead chalcogenides like PbSe and PbS, and more recently perovskite materials,
which are discussed further in the next section. The n-type metal oxide is deposited on
conducting glass (typically FTO or ITO), and a high work function electrode (typically
coated with a HTM) is placed on top. Photons are absorbed by the quantum dots, and elec-
trons and holes are transported by drift and diffusion to the collection electrodes.
A certified efficiency of 13.4% has been obtained with a cell employing CsPbI3 QDs and
the following architecture: FTO/TiO2/CsPbI3 QDs/Spiro-OMeTAD/MoOx/Al [25], where
Spiro-OMeTAD (2,20 ,7,70 -tetrakis-[N,N0 -di-p-methoxyphenylamino]-9,90 -spirobifluorene)
14 ADVANCED MICRO- AND NANOMATERIALS FOR PHOTOVOLTAICS
and MoOx are HTM layers. Recent progress in colloidal quantum dot solar cells, and
related quantum dot sensitized solar cells, is discussed in a review article by Wei et al. [26].
3.4 Perovskite Solar Cells
The solar cells that have received the most attention recently are those based on metal
halide perovskite absorbers. Unlike almost all other types of solar cells, perovskite devices
can be cost-effective, efficient, flexible, and lightweight at the same time. These properties
have let PSCs become a promising candidate to either compete with silicon solar cell tech-
nology or to be coupled with it to produce multijunction devices. A perovskite has ABX3
composition, where A, B, and X are a monovalent cation, a divalent cation, and a mono-
valent anion, respectively. In the perovskite structure, A+ cations occupy the void spaces in
the BX3 inorganic framework. The Goldschmidt tolerance factor determines if a combi-
nation of cations and anions may produce a perovskite structure,
rA + rX
tf ¼ pffiffiffi (6)
2 ðrB + rX Þ
where rA, rB, and rX are the ionic radius of the corresponding ions. A typical tolerance fac-
tor between 0.9 and 1 is favorable and representative of a cubic and compact phase of
perovskite. The first perovskite composition used in PSCs was CH3NH3PbI3. Composi-
tional engineering has shown that either of the three ions may be completely or partially
replaced to achieve a similar or higher device efficiency. Until now, the highest-efficiency
devices have usually been fabricated using the combination of CH3NH3, formamidinium
(FA), and Cs+ as the A-site cation, and I and Br as the X-site anion [27]. Similar to OPVs or
CQDSCs, a perovskite active layer is sandwiched between ETM and HTM layers as shown
in Fig. 7D. Therefore, either of the n-i-p or p-i-n configurations are possible for PSCs,
where n, i, and p are representative of n-doped ETM, intrinsic perovskite, and p-doped
HTM, respectively. One of the outstanding properties of metal halide perovskites is their
low exciton binding energies (i.e., 2–12 meV) [28, 29]. The thermal energy of excitons at
room temperature is kBT 26 meV, where kB is the Boltzmann constant and T is the tem-
perature. Hence, the photoexcited electrons and holes can easily be dissociated into free
carriers inside the perovskite layer. As a result, PSCs are not highly dependent on the large
surface area in the TiO2 layer of DSSCs or the bulk heterojunctions of OPVs.
Improving efficiency and stability are two important strategies to develop the PSC
technology. In terms of efficiency, PSCs have already reached their maximum theoretical
values of Jsc and FF. Therefore, future research should be focused on improving the Voc.
A general approach to this challenge is decreasing the density of trap states. Perovskites
are known to suffer from iodide migration, a phenomenon that occurs when they are illu-
minated or electrically biased. The iodide migration leads to hysteresis of J-V curves, when
they are scanned in reverse and forward directions, and to poor device stability in the long
term. Providing extra iodide atoms while fabricating the perovskite layer was suggested as
a solution to mitigate the iodide migration [30]. This has led to achieving one of the highest
Chapter 1 • Fundamental Understanding of Solar Cells 15
certified efficiencies (22.1%) reported to date. It had a device architecture of FTO/compact
TiO2/mesoporous TiO2/(FA)1 xCsxPbI3 yBry/Poly(triarylamine)/Au. Although the high
efficiencies of PSCs are very close to those of silicon solar cells, their stability needs to
be improved before commercialization. PSCs are susceptible to exposure to humidity
[31] or O2 while under illumination [32]. Research on improving the efficiency or the sta-
bility of PSCs has been based on modifications of the composition [33] or fabrication pro-
cedures for either the perovskite or other layers. A discussion about the efficiency and
stability of PSCs can be found in a review article by Correa-Baena et al. [34].
3.5 Other New Materials and Structures
The development of new photovoltaic materials and cells extends well beyond the DSSCs,
OPV, CQDSCs, and PSCs discussed in this section. Novel materials and designs for photon
converters, tandem cells, and hot carrier cells, among others, continue to be developed to
address the limitations discussed in Section 2. Oxides are used in virtually every emerging
PV architecture of Fig. 7, particularly as selective ETM (e.g., TiO2, SnO2, and ZnO) and
HTM (e.g., MoO3, NiO, and WO3) layers. New methods, such as atmospheric pressure spa-
tial atomic layer deposition (AP-SALD), are being developed to finely tune the properties
of these oxides and manufacture them in a scalable manner. Novel nanostructures are also
being developed for better light management and superior electrical contacts. Promising
TCEs include metal nanowire networks and two-dimensional materials such as graphene,
among others. This text will provide an overview of a variety of these advanced microscale
and nanoscale photovoltaic technologies currently under development.
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