photovoltaic effect, process in which two dissimilar materials in close contact produce an electrical

voltage when struck by light or other radiant energy. Light striking crystals such
as siliconor germanium, in which electrons are usually not free to move from atom to atom within the
crystal, provides the energy needed to free some electrons from their bound condition. Free
electrons cross the junction between two dissimilar crystals more easily in one direction than in the
other, giving one side of the junction a negative charge and, therefore, a negative voltage with
respect to the other side, just as one electrode of a battery has a negative voltage with respect to the
other. The photovoltaic effect can continue to provide voltage and current as long as light continues
to fall on the two materials. This current can be used to measure the brightness of the incident light
or as a source of power in an electrical circuit, as in a solar power system (see solar cell).
The photovoltaic effect in a solar cell can be illustrated with an analogy to a child at a slide. Initially,
both the electron and the child are in their respective ground states. Next, the electron is lifted up to
its excited state by consuming energy received from the incoming light, just as the child is lifted up to
an excited state at the top of the slide by consuming chemical energy stored in his body. In both
cases there is now energy available in the excited state that can be expended. In the absence of
junction-forming materials, there is no incentive for excited, free electrons to move along a specific
direction; they eventually fall back to the ground state. On the other hand, whenever two different
materials are placed in contact, an electric field is generated along the contact. This is the so-called
built-in field, and it exerts a force on free electrons, effectively tilting the electron states and forcing
the excited free electrons into an external electrical load where their excess energy can be
dissipated. The external load can be a simple resistor, or it can be any of a myriad of electrical or
electronic devices ranging from motors to radios. Correspondingly, the child moves to the slide
because of his desire for excitement. It is on the slide that the child dissipates his excess energy.
Finally, when the excess energy is expended, both the electron and the child are back in the ground
state, where they can begin the whole process over again. The motion of the electron, like that of the
child, is in one direction. In short, the photovoltaic effect produces a direct current (DC)one that
flows constantly in only a single direction. See alsophotoelectric effect.
An organic solar cell or plastic solar cell is a type of polymer solar cell that uses organic
electronics, a branch of electronics that deals with conductive organic polymers or small organic
molecules,[1] for light absorption and charge transport to produceelectricity from sunlight by
the photovoltaic effect.
The plastic used in organic solar cells has low production costs in high volumes. Combined with the
flexibility of organicmolecules, organic solar cells are potentially cost-effective for photovoltaic
applications. Molecular engineering (e.g. changing the length and functional group of polymers) can
change the energy gap, which allows chemical change in these materials. Theoptical absorption
coefficient of organic molecules is high, so a large amount of light can be absorbed with a small

amount of materials. The main disadvantages associated with organic photovoltaic cells are
low efficiency, low stability and low strength compared to inorganic photovoltaic cells.
Contents
[hide]

Physics[edit]

Fig 1: Examples of organic photovoltaic materials

A photovoltaic cell is a specialized semiconductor diode that converts visible light into direct
current (DC) electricity. Some photovoltaic cells convert infrared (IR) or ultraviolet (UV) radiation into
DC. A common characteristic of both the small molecules and polymers (Fig 1) used
in photovoltaics is that they all have large conjugated systems. A conjugated system is formed
where carbon atoms covalently bond with alternating single and double bonds; in other words these
are chemical reactions of hydrocarbons. These hydrocarbons' electrons pz orbitals delocalize and
form a delocalized bonding orbital with a * antibonding orbital. The delocalized orbital is the
highest occupied molecular orbital (HOMO), and the * orbital is the lowest unoccupied molecular
orbital (LUMO). The voltage separation between HOMO and LUMO is considered the band gap of
organic electronic materials. The band gap is typically in the range of 14 eV.[2]
When these materials absorb a photon, an excited state is created and confined to a molecule or a
region of a polymer chain. The excited state can be regarded as an electron-hole pair bound
together by electrostatic interactions, i.e. excitons. In photovoltaic cells, excitons are broken up into
free electron-hole pairs by effective fields. The effective fields are set up by creating a heterojunction
between two dissimilar materials. Effective fields break up excitons by causing the electron to fall

from the conduction band of the absorber to the conduction band of the acceptor molecule. It is
necessary that the acceptor material has a conduction band edge that is lower than that of the
absorber material.[3][4][5][6]

Junction types[edit]
Single layer[edit]

Fig 2: Sketch of a single layer organic photovoltaic cell

Single layer organic photovoltaic cells are the simplest form. These cells are made by sandwiching a
layer of organic electronic materials between two metallic conductors, typically a layer of indium tin
oxide (ITO) with high work function and a layer of low work function metal such as Aluminum,
Magnesium or Calcium. The basic structure of such a cell is illustrated in Fig 2.
The difference of work function between the two conductors sets up an electric field in the organic
layer. When the organic layer absorbs light, electrons will be excited to the LUMO and leave holes in
the HOMO, thereby forming excitons. The potential created by the different work functions helps to
split the exciton pairs, pulling electrons to the positive electrode (an electrical conductor used to
make contact with a non-metallic part of a circuit) and holes to the negative electrode. [3][4][5]
Examples[edit]
In 1958 the photovoltaic effect or the creation of voltage of a cell based on
magnesium phthalocyanine (MgPc)a macrocyclic compound having an alternating nitrogen atomcarbon atom ring structurewas discovered to have a photovoltage of 200 mV.[7] An Al/MgPc/Ag cell
obtained photovoltaic efficiency of 0.01% under illumination at 690 nm.[8]
Conjugated polymers were also used in this type of photovoltaic cell. One device. used
polyacetylene (Fig 1) as the organic layer, with Al and graphite, producing an open circuit voltage of
0.3 V and a charge collection efficiency of 0.3%.[9] An Al/poly(3-nethyl-thiophene)/Pt cell had an
external quantum yield of 0.17%, an open circuit voltage of 0.4 V and a fill factor of 0.3.[10] An
ITO/PPV/Al cell showed an open circuit voltage of 1 V and a power conversion efficiency of 0.1%
under white-light illumination.[11]

Issues[edit]
Single layer do not work well. They have low quantum efficiencies (<1%) and low power conversion
efficiencies (<0.1%). A major problem with them is that the electric field resulting from the difference
between the two conductive electrodes is seldom sufficient to split the excitons. Often the electrons
recombine with the holes without reaching the electrode.

Bilayer[edit]

Fig 3: Sketch of a multilayer organic photovoltaic cell.

Bilayer cells contain two layers in between the conductive electrodes (Fig 3). The two layers have
different electron affinity and ionization energies, therefore electrostatic forces are generated at the
interface between the two layers. The materials are chosen to make the differences large enough
that these local electric fields are strong, which splits excitons much more efficiently than single layer
photovoltaic cells. The layer with higher electron affinity and ionization potential is the electron
acceptor, and the other layer is the electron donor. This structure is also called a planar donoracceptorheterojunction.[3][4][5][6]
Examples[edit]
C60 has high electron affinity, making it a good acceptor. A C60/MEH-PPV double layer cell had a
relatively high fill factor of 0.48 and a power conversion efficiency of 0.04% under monochromatic
illumination.[12] PPV/C60 cells displayed a monochromatic external quantum efficiency of 9%, a power
conversion efficiency of 1% and a fill factor of 0.48. [13]
Perylene derivatives display high electron affinity and chemical stability. A layer of copper
phthalocyanine (CuPc) as electron donor and perylene tetracarboxylic derivative as electron
acceptor, fabricating a cell with a fill factor as high as 0.65 and a power conversion efficiency of 1%
under simulated AM2 illumination.[14] Halls et al. fabricated a cell with a layer of bis(phenethylimido)
perylene over a layer of PPV as the electron donor. This cell had peak external quantum efficiency of
6% and power conversion efficiency of 1% under monochromatic illumination, and a fill factor of up
to 0.6.[15]

Issues[edit]
The diffusion length of excitons in organic electronic materials is typically on the order of 10 nm. In
order for most excitons to diffuse to the interface of layers and split into carriers, the layer thickness
should be in the same range as the diffusion length. However, a polymer layer typically needs a
thickness of at least 100 nm to absorb enough light. At such a large thickness, only a small fraction
of the excitons can reach the heterojunction interface.

Discrete heterojunction[edit]
A three-layer (two acceptor and one donor) fullerene-free stack achieved a conversion efficiency of
8.4%. The implementation produced high open-circuit voltages and absorption in the visible spectra
and high short-circuit currents. Quantum efficiency was above 75% between 400 nm and 720 nm
wavelengths, with an open-circuit voltage around 1 V.[16]

Bulk heterojunction[edit]

Fig 4: Sketch of a dispersed junction photovoltaic cell

In bulk heterojunction cells, the electron donor and acceptor are mixed, forming a polymer blend (Fig
4). If the length scale of the blend is similar to the exciton diffusion length, most of the excitons
generated in either material may reach the interface, where excitons split efficiently. Electrons move
to the acceptor domains then were carried through the device and collected by one electrode, and
holes move in the opposite direction and collected at the other side. [4][5][7]
Most bulk heterojunction cells use two components, although three-component cells have been
explored. The third component, a secondary p-type donor polymer, acts to absorb light in a different
region of the solar spectrum. This in theory increases the amount of absorbed light. These ternary
cells operate through one of three distinct mechanisms: charge transfer, energy transfer or parallellinkage.
In charge transfer, both donors contribute directly to the generation of free charge carriers. Holes
pass through only one donor domain before collection at the anode. In energy transfer, only one
donor contributes to the production of holes. The second donor acts solely to absorb light,
transferring extra energy to the first donor material. In parallel linkage, both donors produce excitons
independently, which then migrate to their respective donor/acceptor interfaces and dissociate. [17]

Examples[edit]
C60 and its derivatives are used as electron acceptors, as in dispersed heterojunction photovoltaic
cells. A cell with the blend of MEH-PPV and a methano-functionalized C60 derivative as the
heterojunction, ITO and Ca as the electrodes[18] showed a quantum efficiency of 29% and a power
conversion efficiency of 2.9% under monochromatic illumination. Replacing MEH-PPV
with P3HT produced a quantum yield of 45% under a 10 V reverse bias.[19][20]
Polymer/polymer blends are also used in dispersed heterojunction photovoltaic cells. A blend of CNPPV and MEH-PPV with Al and ITO as the electrodes, yielded peak monochromatic power
conversion efficiency of 1% and fill factor of 0.38.[21][22]
Dye sensitized photovoltaic cells can also be considered important examples of this type.

Graded heterojunction[edit]
The electron donor and acceptor are mixed in such a way that the gradient is gradual. This
architecture combines the short electron travel distance in the dispersed heterojunction with the
advantage of the charge gradient of the bilayer technology.[23][24]
Examples[edit]
A cell with a blend of CuPc and C60 showed a quantum efficiency of 50% and a power conversion
efficiency of 2.1% using 100 mW/cm2 simulated AM1.5G solar illumination for a graded
heterojunction.[25]

Current challenges and recent progress[edit]

Difficulties associated with organic photovoltaic cells include their low external quantum efficiency
(up to 70%)[26] in comparison with inorganic photovoltaic devices; due largely to the large band gap of
organic materials. Instabilities against oxidation and reduction, recrystallization and temperature
variations can also lead to device degradation and decreased performance over time. This occurs to
different extents for devices with different compositions, and is an area into which active research is
taking place.[27]
Other important factors include the exciton diffusion length; charge separation and charge collection;
and charge transport and mobility, which are affected by the presence of impurities.

Effect of film morphology[edit]

Fig 5: Highly folded heterojunction (a); heterojunction with controlled growth (b)

As described above, dispersed heterojunctions of donor-acceptor organic materials have high

quantum efficiencies compared to the planar hetero-junction, because in dispersed heterojunctions it
is more likely for an exciton to find an interface within its diffusion length. Film morphology can also
have a drastic effect on the quantum efficiency of the device. Rough surfaces and the presence of

voids can increase the series resistance and also the chance of short-circuiting. Film morphology
and, as a result, quantum efficiency can be improved by annealing of a device after covering it by a
~1000 thick metal cathode. Metal film on top of the organic film applies stresses on the organic
film, which helps to prevent the morphological relaxation in the organic film. This gives more densely
packed films and at the same time allows the formation of phase-separated interpenetrating donoracceptor interface inside the bulk of organic thin film.[28]

Controlled growth heterojunction[edit]

Charge separation occurs at the donor acceptor interface. Whilst traveling to the electrode, a charge
can become trapped and/or recombine in a disordered interpenetrating organic material, resulting in
decreased device efficiency. Controlled growth of the heterojunction provides better control over
positions of the donor-acceptor materials, resulting in much greater power efficiency (ratio of output
power to input power) than that of planar and highly disoriented hetero-junctions (as shown in Fig 5).
Thus, the choice of suitable processing parameters in order to better control the structure and film
morphology is highly desirable.[17]

Progress in growth techniques[edit]

Mostly organic films for photovoltaic applications are deposited by spin coating and vapor-phase
deposition. However each method has certain draw backs, spin coating technique can coat larger
surface areas with high speed but the use of solvent for one layer can degrade the already existing
polymer layer. Another problem is related with the patterning of the substrate for device as spincoating results in coating the entire substrate with a single material.

Vacuum thermal evaporation[edit]

Fig 6: Vacuum thermal evaporation (a) and organic phase vapor deposition (b)

Another deposition technique is vacuum thermal evaporation(VTE) which involves the heating of an
organic material in vacuum. The substrate is placed several centimeters away from the source so
that evaporated material may be directly deposited onto the substrate, as shown in Fig 6(a). This
method is useful for depositing many layers of different materials without chemical interaction
between different layers. However, there are sometimes problems with film-thickness uniformity and
uniform doping over large-area substrates. In addition, the materials that deposit on the wall of the
chamber can contaminate later depositions. This "line of sight" technique also can create holes in
the film due to shadowing, which causes an increase in the device series-resistance and short
circuit.[29]

Organic vapor phase deposition[edit]

Organic vapor phase deposition (OVPD, Fig 6(b)) allows better control of the structure and
morphology of the film than vacuum thermal evaporation. The process involves evaporation of the
organic material over a substrate in the presence of an inert carrier gas. The resulting film
morphology can be tuned by changing the gas flow rate and the source temperature. Uniform films
can be grown by reducing the carrier gas pressure, which will increase the velocity and mean free
path of the gas, and as a result boundary layer thickness decreases. Cells produced by OVPD do

not have issues related with contaminations from the flakes coming out of the walls of the chamber,
as the walls are warm and do not allow molecules to stick to and produce a film upon them.
Another advantage over VTE is the uniformity in evaporation rate. This occurs because the carrier
gas becomes saturated with the vapors of the organic material coming out of the source and then
moves towards the cooled substrate, Fig. 6(b). Depending on the growth parameters (temperature of
the source, base pressure and flux of the carrier gas) the deposited film can be crystalline or
amorphous in nature. Devices fabricated using OVPD show a higher short-circuit current density
than that of devices made using VTE. An extra layer of donor-acceptor hetero-junction at the top of
the cell may block excitons, whilst allowing conduction of electron; resulting in improved cell
efficiency.[29

Advantages of Flexible Organic Compared to Rigid Conventional Solar

Cells
The latest advances in molecular engineering have uncovered a series of organic cell
potential advantages that may eventually outbalance the benefits of silicon based solar
cells. Although conventional solar cells currently dominate the existing market, the case may
be quite different in the near future.
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Manufacturing Process & Cost

Organic solar cells can be easily manufactured compared to silicon based cells, and this is
due to the molecular nature of the materials used. Molecules are easier to work with and can
be used with thin film substrates that are 1,000 times thinner than silicon cells (order of a
few hundred nanometers). This fact by itself can reduce the cost production significantly.
Since organic materials are highly compatible with a wide range of substrates, they present
versatility in their production methods. These methods include solution processes (inks or
paints), high throughput printing techniques, roll-to-roll technology and many more, that
enable organic solar cells to cover large thin film surfaces easily and cost-effectively. All
above methods have low energy and temperature demands compared to conventional
semiconductive cells and can reduce cost by a factor of 10 or 20.

Tailoring Molecular Properties

An important advantage of organic materials used in solar cell manufacturing is the ability to
tailor the molecule properties in order to fit the application. Molecular engineering can
change the molecular mass, bandgap, and ability to generate charges, by modifying e.g. the

length and functional group of polymers. Moreover, new unique formulations can be
developed with the combination of organic and inorganic molecules, making possible to print
the organic solar cells in any desirable pattern or color.

Desirable Properties
The tailoring of molecular properties and the versatility of production methods described on
the previous page enable organic polymer solar cells to present a series of desirable
properties. These solar modules are amazingly lighter and more flexible compared to their
heavy and rigid counterparts, and thus less prone to damage and failure. They can exist in
various portable forms (e.g. rolled form) and their flexibility makes storage, installation, and
transport much easier.

Environmental Impact
The energy consumed to manufacture a solar cell is less than the amount required for
conventional inorganic cells. Consequently, the energy conversion efficiency doesn't have to
be as high as the conventional cell's efficiency. An extensive use of organic solar cells could
contribute to the increased use of solar power globally and make renewable energy sources
friendlier to the average consumer.

Multiple Uses and Applications

The present situation indicates that organic solar cells cannot substitute for silicon cells in
the energy conversion field. However their use seems to be more targeted towards specific
applications such as recharging surfaces for laptops, phones, clothes, and packages, or to
supply the power for small portable devices, such as cellphones and MP3 players.
Other than the domestic use, recent developments have shown a military application
potential for organic solar modules. Research in the US (Konarka) has shown that organic
cells can be used in soldier tents to generate electricity and supply power to other military
equipment such as night vision scopes and GPS (global positioning system) receivers. This
technology is thought to be extremely valuable for demanding missions.

The Current Situation

Organic Solar cells have certain disadvantages including their low efficiency (only 5%
efficiency compared to the 15% of silicon cells) and short lifetime. Nonetheless, their
numerous benefits can justify the current international investment and research in
developing new polymeric materials, new combinations, and structures to enhance

efficiency and achieve low-cost and large-scale production within the next years. A
commercially viable organic solar cell production is the target of the next decade.