1.

INTRODUCTION-PROBLEM DEFINITION

1.1 Energy:

Energy is defined as, Capacity of a physical system to perform work. It is a globally conserved quantity i.e., the total amount of energy in the universe is constant. Energy neither be created nor destroyed. It can only be transformed from one from to another. e.g., a solar cell illustrates the conversion of light energy to electrical energy; a battery converts chemical energy into electrical energy.

Energy, environment and economic development are closely related. The proper use of energy requires consideration of social impact as well as technological ones. Indeed, sustained economic growth of a country in this century along with improvements in the quality of everyones lives may be possible only be the well planned and efficient use of fossil fuel and other resources and the development of new renewable energy technologies. Thus, the energy which is used by the human beings on planet Earth can be classified as (i) renewable energy sources and (ii) nonrenewable energy sources.
(1)

1.1.1 Renewable energy sources: The energy sources which are derived from natural sources that replenish themselves over short period of time. Renewable energy sources include hydropower (Tidal energy and wave power), geothermal energy, wind energy, solar energy, and bio-mass energy. These resources are also called nonconventional sources of energy.

1.1.2

Non-renewable energy sources:

These are the energy sources that are derived from finite and static stocks of energy. It cannot be produced, grown, generated or used on a scale that can sustain its consumption rate. Due to its exhaustibility in nature, these types of energy resources are sometimes also called conventional sources of energy. Examples of these types of resources are fossil fuels such as; coal, petroleum, natural gas and nuclear power.

Since all the conversion sources of energy are limited and they cannot be reproduced. So, the limited supply of todays main energy sources (oil, coal, uranium) will force ussooner or later to replace most of the currently used power plants with renewable energy sources. According to recent predictions, the inevitable permanent decline in the global oil production rate is expected to start within the next 10-20 years.
(2)

Worldwide oil prices will then rise considerably favoring the introduction of various renewable energy sources such as the direct conversion of solar energy (solar cells).

Figure 1.1: The atmospheric concentration of greenhouse gases like CO2 has grown significantly since pre-industrial times. This can be largely attributed to human activities, mostly fossil-fuel use. Dashed lines are possible (optimistic) future scenarios.
(3)

However, the combustion of fossil fuels in the past has already harmful effects on the delicate balance of nature on our planet Earth. Today, about 20 x 1012 kg of carbon di-oxide is put into the atmosphere every year, mainly by burning fossil fuels as depicted in figure 1.1.

Todays plants are unable to absorb this huge amount of extra CO2. As a result the CO2 concentration in the atmosphere
3

continues to mount adding considerably to the greenhouse effect which will increase the global mean surface temperature depending on future emission scenarios and the actual climate sensitivity by the year 2100.

Global mean surface temperature has increased by 0.3-0.6C since the late 19th century and the global sea level has risen by 10-25 cm, most likely due to human activities. The consequences of this temperature change have already increased the frequency and severity of natural disasters and are likely to have more devastating effects for humans and other life forms in all parts of earth within the next decades.(4)

Fortunately, we have renewable energy sources which neither run out nor have any significant harmful effects on our environment.

All renewable energy sources (apart from tidal and geothermal energy) are powered by a steady flux of energy from the sun. The total flux amounts to approximately 1.7 1017 W, which is more than 50 thousand times the rate at which energy is produced and consumed by mankind.

The intensity of sunlight just outside the atmosphere is 1366 W/mt2 (the solar constant). On the way down the atmosphere, some of the radiation is reflected back into space and a part of energy is absorbed in clouds and the air mass. The absorbed energy drives the dynamics of the atmosphere from which energy
4

can be tapped as wind or wave energy. The amount of solar irradiation that reaches the ground amounts to 160 W/mt2, averaged over time and the surface of the earth. This number is put into perspective by the following citations from an essay by Denis Hayes:

The sunlight that fall on the roads in the US last year contained roughly as much energy as in all the fossil fuel consumed last year in the world.

No country uses as much energy as is contained in the sunlight that strikes its buildings.

The quotations underlines that solar power is an abundant resource that has the potential for playing a major role in the worlds energy supply. As it is furthermore universally available (although to a varying extent), it may also play a key role in bringing electric power to areas where an electric grid has not yet been established. (5)

Presently, even though commercial energy sources like coal, oil, and natural gas are being utilized to a large extent, renewable sources of energy are slowly gaining importance. Renewable energy plays a basic role in sustainable development. Such sources can supply the energy we need for indefinite periods of time polluting far less than fossil fuels.

The advantages of renewables are well known, as far as they enhance diversity in energy supply markets; secure long-term sustainable energy supplies; reduce local and global atmospheric emissions; and create new employment opportunities, offering possibilities for local manufacturing.

According to the International Energy Agency (IEA), renewable energy includes hydropower, biomass, and wind, solar, geothermal and marine energy. Figure 1.2 shows the world share of total primary energy consumption (TPES) from 1997. Figure 1.2 shows that renewable energy represented 13.4% of total world combustion in 1973 which increased up to 18.7% in 2008 as shown by Figure 1.3.
Hydro, 1.80% Nuclear, 0.90% Combustible renewable & waste, 10.60% Geothermal,sol ar,wind, 0.10%

Gas, 16%

Coal/peat, 24.50% Oil, 46.10%

Figure 1.2: World shares of total primary energy supply (TPES) in 1973.

Nuclear, 5.80%

Hydro, 2.20% Combustible renewable & waste, 10% Geothermal,sol ar,wind, 0.70%

Gas, 21.10% Coal/peat, 27%

Oil, 33.20%

Figure 1.3: World shares of total primary energy supply (TPES) in 2008.

1.2

Solar Cell:

It is expected that, renewable energy is one of the challenges to society in the 21st century. One of the renewable energy technologies is photovoltaic (PV), the technology that directly coverts daylight into electricity. PV is one of the fastest growing of all the renewable energy technologies; in fact, it is one of the fastest growing industries at present.
(6)

The solar cell found

applications in customer electronics, small scale remote residential power systems, as well as in communication and signaling. However, it is only in the second half of last decade that grid connected photovoltaic (PV) systems entered the market with significant contribution as a result of the intensive roof programs in Japan, Germany and US. Todays photovoltaic market has exceeded 200MW per year and the market growth has been between 15% and 20% in the last decade. In 2000 the production of PV panels exceeded 280 MW, and has been forecasted to surpass 350 MW in 2001 (solar Access 2001c). According to market

forecasts predicting an average growth of about 25% world PV market could reach 550 MW in 2005 and 1700MW in 2010. solar cells are mainly categorized in two types.
(7)

The

1.2.1 Inorganic Solar Cell:

At present, the active material used for the fabrication of solar cells are mainly inorganic materials, such as silicon (Si), galliumarsenide (GaAs), cadmium-telluride (CdTe) and cadmium-indiumselenide (CTS). The power conversion efficiency for these solar cells varies from 8 to 29% (Table-1.1). The silicon solar cell is the traditional solar cell and found applications in various areas such as calculators, garden lamps and roof mounted large area cells etc. The silicon solar cell (SSC) has so far been the best candidate for conversion of sunlight and therefore the development and research of solar cells has been dominated by this.

Semiconductor Material Mono Crystalline Silicon Poly Crystalline Silicon Gallium-Arsenide Amorphous Silicon Cadmium Telluride Cadmium Indium Selenide

Power Conversion Efficiency (%) 20-24 13-18 20-29 8-13 10-17 10-19

Technology Crystalline Thick and Thin Film Crystalline Thin Film Thin Film Thin Film

Table (1.1): States of power conversion efficiencies in February 2002, as reached for inorganic solar cells and the technology used to prepare these solar cells. Source: Photovoltaic Network for the development of roadmap for photovoltaic (PV-NET).

Silicon solar cells trace their history back to the 1950s where the first silicon solar cell was reported by Chapin, Fuller and Pearson. It had a power conversion efficiency of 6%. silicon solar cells dominated the
(8)

Up to 2001, the market by

photovoltaic

82%(Figure 1.4) and the recorded efficiency for a laboratory cell was 24.7% while the efficiency of the commercial crystalline silicon solar panels was in the best case about 15%.

World PV Market
50 45 40 35 30 25 20 15 10 5 0 Single Crystal Si 39 Amorphous Si 13 Polycrystalli ne Si 43

Ribbon Si 3

Thin Film Si 1

CdTe 1

Series1

Figure1.4: World photovoltaic market in 1998 by technologies.

The main reason why Si has dominated the PV market is that high quality Si has been already produced at large quantities by the semiconductor industry. The processing of crystalline silicon wafers is high-level semiconductor technology, and such expensive and very capital intensive. This also adds directly to the
9

cost of the photovoltaic modules, so that the cost of processed silicon wafers contribute to 50% of the total manufacturing cost of the module.

A big question for the photovoltaic technology is the availability of highly purified Si. The PV industry has been using mainly low cost reject material from the semiconductor industry. This has created a problematic dependence on the volatile semiconductor market causing fluctuations also in the cost of Si material for the solar cells. (7) The price per watt was very high, being as much as $200 per watt. This meant that silicon solar cells were not seriously considered as an everyday power source for many decades, only in very remote places and if the costs were made unimportant by the benefits of silicon solar cells such as satellites.
(9) (8)

e.g. Conventional solar cells

were first commercialized in the 1960s for use in space program

Silicon solar cells has benefited from the fast development in the integrated circuit industry, and this means that it is now possible to produce silicon solar cells with efficiencies as high as 25%, and at a much lower cost than previously. The prices for solar cell power today lies approximately $10 and 12 per watt, based on todays prices on the internet.(8)

In fact, it is generally seen that the dominance of the standard Si PV technology in the growing PV market can be realized only by the production of special solar cell grade silicon. Yet the first efforts to produce such material have been unsuccessful because
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of the high purity requirements and the small market for the special silicon at the moment. The current status of photovoltaic is that it hardly contributes to the energy market, because it is far too expensive. Although the manufacturing costs of silicon solar cells have dropped dramatically, but the cost are still too high for large scale energy production. It seems to be generally understood however, that the cost reduction can be achieved only by increasing manufacturing volume. From the manufacturing point of view this is coupled to the need for the special solar cell grade supply and from the markets point of view not very easy to achieve at
(10)

present

PV

system

costs

without

governmental

subsidies.

The large production costs for the silicon solar cells are one of the major obstacles. Even when the production costs could be reduced, large scale production of the current silicon solar cells would be limited by the scarcity of some elements required; e.g., solar grade silicon. To ensure a sustainable technology path for photovoltaic, for reduce the costs of the current silicon technology need to be balanced with measure to create and sustain variety in photovoltaic technology. It is, therefore, clear that techno diversity, implying new solar cell technologies, is necessary.
(11)

1.2.2 Organic Solar Cell:

Organic electronic materials are of interest for future applications in solar cells. This is due partly to the rapid growth of the photovoltaic market, which has stimulated research into longer
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term, more innovative photovoltaic technologies, and partly to the development applications. of organic electronic materials for display

Organic materials are attractive for photovoltaic primarily through the prospect of high throughput manufacture using reel-to-reel or spray deposition. Additional attractive features are the possibilities for ultra-thin, flexible devices which may be integrated into appliances or building materials and tuning of color through chemical structure. The field has made impressive progress in the last 5 years. Solar power conversion efficiencies of over 2% have now been reported for four distinct classes of organic solar cell, a growing range of new photovoltaic materials have been studied and increasing numbers of academic research groups
(12)

and

companies have declared an interest in soft solar cells.

Latest advances have shown a great potential for organic solar cells compared to conventional silicon solar cells. Their versatility in production methods, properties and applications looks very promising for the future of solar energy.

1.3 Advantages of Flexible Organic compared to Rigid Conventional Solar Cells:

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

1.3.1 Manufacturing Process & Cost:

OPV can be easily manufactured compared to SSC, 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 1000 times thinner than SSC (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 SSCs and can reduce the cost by a factor of 10 or 20.

1.3.2 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
13

combination of organic and inorganic molecules, making possible to print the organic solar cells in any desirable pattern or color.

1.3.3 Environmental Impact:

The energy consumed to manufacture a solar cell is less than the amount required for conventional inorganic cells. 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.

Organic solar cells have certain disadvantages including their low efficiency and short life time. Nevertheless, 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 is the target of the next decade.
(13)

1.4 Classification of organic solar cell:

In present time, organic solar cells are classified into four categories on the basis of their architectures. This classification is shown by the figure 1.5 and gives brief introduction of each class.

14

Organic Solar Cell

Single Layer

Double Layer

Bulk Hetero junction

Laminated

Figure 1.5 Types of Architecture for organic solar cell. 1.4.1 Single layer Photovoltaic Cells:

The first generation of organic photovoltaic cells a single layer of pure conjugated polymer were sandwiched between two metal electrodes of different work functions such as ITO and Al, Ca or Mg. The layout of this structure is shown in figure 1.6. The dissimilarity of the work functions of the electrodes in these photovoltaic cells is essential. Upon short-circuiting the device, electrons move from the low work function electrode (Al, Ca or Mg) to the high work function electrode (ITO) creating an electric field across the polymer layer (7). The rectifying behavior of these devices can be explained by the MIM-model (for insulator) or by the formation of a Schottky barrier (for doped materials) between the metal with the lower work function and p-type organic layer
(14)

. Hence, single layer PV cells

are usually referred to as Schottky diodes since charge separation occurs at the rectifying (Schottky) junction with one electrode. Therefore, the photoactive region is very thin (near the rectifying contact) and, since both positive and negative photoexcited charges travel through the same material, recombination losses are high
(15)

. The power conversion efficiency reported were generally

very low (16).

15

Al Active layer ITO Glass

Figure 1.6 Single layer organic solar cells. 1.4.2 Bi-Layer Heterojunction Photovoltaic Cells:

In 1986, a major breakthrough was realized by C.W. Tang, who introduced a bi-layer
(17)

structure

of

p-type

and

n-type

semiconductor

. In a bi-layer heterojunction PV cell, p-type and

n-type organic semiconductors are sandwiched between two electrodes matching the donor HOMO and the acceptor LUMO, for efficient extraction of the corresponding charge carriers. In these cells, p-type semiconductor is served as an electron donor while the n-type semiconductor is served as electron-acceptor
(18)

.The

bi-layer cell structure is schematically depicted in figure 1.7. The charge transfer in bi-layer heterojunction between undoped donor and acceptor materials is due to the differences in the ionization potential and the electron affinity of the adjacent materials. Upon photon absorption in the donor D, the electron is excited from the HOMO to the LUMO. If now an acceptor molecule A is in the close proximity, the electron may be transferred to the LUMO of A; which is energetically preferential when, ID* - AA - UC < 0 Where, ID* is the ionization potential of the excited state (D*) of the donor; AA the electron affinity of the acceptor, and UC the effective Coulomb interaction respectively (18, 14).
16

Al A D ITO Glass
Figure 1.7 Schematic diagram of bi-layer organic solar cell.

1.4.3

Bulk-Heterojunction Photovoltaic Cells:

Photovoltaic devices prepared from blends of conjugated polymers and fullerene derivatives are promising candidates for solar energy conversion due to their mechanical flexibility, lightweight, and potential low cost of fabrication of large areas
(19)

. In bulk
(20)

heterojunction, the donor and acceptor species are blended together in a common solvent and deposited simultaneously the bulk of the material
(9)

By mixing the p-type and n-type materials, junctions throughout are created that ensure each photogenerated exciton leads to charge transfer, irrespective of the thickness of the layer .Because holes are transported by the p-type semiconductor and electrons by the n-type semiconductor, these materials should be preferably mixed into a bicontinuous, interpenetrating network. Schematically diagram of a bulk heterojunction photovoltaic cell is shown in figure 1.8.

17

The bulk heterojunction is presently the most widely used photoactive layer for realization of organic solar cells. The name bulk-heterojunction photovoltaic cell has been chosen, because the interface between two different components (heterojunction) is all over the bulk, in contrast to the classical (bi-layer) junction
(20)

. Control of morphology is not only required for a large charge-

generating interface and suppression of exciton loss, but also to ensure percolation pathways for both electron and hole transport to the collecting electrodes
(21, 22)

Al A+D ITO Glass

Figure 1.8 Schematic diagram of bulk heterojunction photovoltaic

cell.

1.4.4 Laminated Photovoltaic Cells:

This relatively recent type represents the successful attempt to unify the advantages of the above structures. Charge separation occurs in the blend layer in the middle that is obtained after laminating the two separate layers together and charge transport
18

can only occur via the correct transport layer. This structure also features the useful options to treat each layer separately (e.g. doping, physical/chemical conversion) before forming the blend layer and instant encapsulation between the two substrates. Hence, the laminated structure of PV cells can be seen as a hybrid between bi-layer and bulk-heterojunction
(4)

. Figure 1.9 is shown

the laminated structure of photovoltaic cell.

Glass Al A A+D D ITO Glass

Figure 1.9 Laminated layer structure of organic photovoltaic cell.

1.5 Organic Photovoltaic Materials:

The current organic photovoltaic materials can be classified in to three different categories, according to their mechanical or processing properties: insoluble, soluble or liquid crystalline (figure 1.10). They can be further divided into molecules with few (oligomers) or single (monomer) structural repeat units, and
19

molecules (polymers) with more than about 10 repeat units. Oligomers are monomers that absorbs in the visible light are also called chromospheres and are referred to as dyes, if they are soluble or pigments, if are not.

Organic Semiconducting Materials

Insoluble

Soluble

Liquid Crystalline

Pigments

Dyes

Dyes

Polymers

Polymers

Polymers

FiFigure 1.10 Classification of organic photovoltaic materials.

1.5.1 Polymers:

The word polymer is derived from the Greek words -poly meaning many, and - meros meaning part. Thus, polymer is a large molecule composed of repeating structural unit. These subunits are typically connected by covalent chemical bonds. Although the term polymer is sometimes taken to, refer to plastics. Polymers or plastics have been traditionally considered passive materials and the electronic industry has been extensively
20

using them as insulators of metallic conductors, photoresists, and encapsulation layers

(23)

1.5.2 Conducting Polymer:

Conducting polymers generally exhibit an alternating single bond double bond structure (conjugation) based on sp2-hybridized carbon atoms. This leads to a highly delocalized -electron system with large electronic polarizability. This enables both absorption within the visible light region, due to -* transitions between the bonding and antibonding pZ orbitals, that and electrical to be charge by transporttwo requirements need met

semiconductors for power generation in solar cells. The Peierls Instability splits the originally half-filled pZ band into two, the and * bands. Upon light absorption electrons may be excited from the bonding into the antibonding * band. This absorption corresponds to the first optical excitation from the HOMO to the LUMO
(24)

The energy difference between the highest occupied states in the -band and the lowest unoccupied state in the *-band is the * energy gap, Eg. Consequently, since there are no partially filled bands, conjugated polymers are typically semiconductors. Because Eg depends upon the molecular structure of the repeat unit, synthetic chemists are provided with the opportunity and the challenge to control the energy gap by design at molecular level
(25)

.Conjugated polymer can be used as either electron donor or

electron acceptor materials in the organic solar cells. 1.6 Excitons:

21

When an electron is jumped from the HOMO into the LUMO, it leaves a hole. These two charges are bound together to form an exciton. Alternatively, an exciton can be thought of as a positive and negative polaron bound by Coulomb interactions. Both singlet (where spins are anti-parallel) and triplet (spins parallel) excitons can exist, but for photovoltaic applications singlet excitons are of most interest. This is because photo-excitations produce singlet excitons due to conservation of spin
(26)

1.7 Doping:

The conductivity of a polymer can be increased several-fold by doping of it with oxidative/reductive (PA) 9-13 with metallic of substituents regimes or by its is donor/acceptor radicals. Shirakawa et al. discovered that doping polyacetylene by increases Doping conductivity orders magnitudes.

accomplished by chemical methods of direct exposure of the conjugated polymer to a charge transfer agent (dopant) in the gas or solution phase, or by electrochemical oxidation or reduction orders of magnitude which can be obtained by doping
(28) (27)

Figure 1.11 shows the increase in electrical conductivity of many .

22

S/cm
106

Doped trans (CH)x 105 S/cm

105 10
4

Ag, Cu Fe, Mg

Metals

103

Doped Polyaniline 103 S/cm

102 101 100

Ge

Undoped trans (CH)x 105 S/cm

10-2 10
-4

Semimetals

10-6

Undoped Polyaniline 10-5S/cm

10-8 10
-10

10-12 10-14 10-16 10-18 10-20

Si AgBr Glass Diamond Nylon Quartz

Insulators

Figure 1.11 Conductivity of electronic polymers, Conductivity increases

with increased doping.

1.8 Basic Working Principles for Photovoltaic Effects:

23

The process of converting light into electric current in an organic photovoltaic cell is accomplished by the following consecutive step. (i) (ii) (iii) (iv) (v) (vi) Absorption of photons Reflection Exciton diffusion Charge separation Charge transport Charge collection

A more detailed analysis permits us to understand and eventually improve the different steps of photovoltaic effect gives the layout of this process.
(29)

. Figure 1.12

1.8.1 Absorption of photons:

In most organic devices only a small portion of the incident light is absorbed because the semiconductor bandgap is too high. A bandgap of 1.1 eV (1100 nm) is required to absorb 77% of the solar radiation on earth whereas the majority of semiconducting polymers have bandgaps higher than 2.0 eV (600 nm), limiting the possible absorption to about 30%. The organic layer is too thin. Low charge carrier and exciton mobilities require layer thickness in the order of 100 nm. Fortunately the absorption coefficient of organic materials is generally much higher than in silicon, so that only about 100 nm thickness is necessary to

24

absorb between 60% and 90%, if a reflective back contact is used.

Absorption of Light

Generation of Exciton

Diffusion of Excitons

Non-radiative relaxation

Transport of exactions to a charge transfer height in the cell bsorption of Light Transport of exactions to a charge transfer height in the cebsorption of Light Transport of carriers to the electrons

Geminate recombination

Charge recombination

Transfer of electrons to the electrodes

Figure 1.12 Conduction mechanisms in organic photovoltaic.

25

1.8.2 Reflection:

Reflection losses are probably significant but little investigated in these materials. Systematic measurements of photovoltaic materials are desired to provide knowledge of their impact on absorption losses. Anti-reflection coatings as used in inorganic devices may then prove useful once other losses such as recombination become less dominant.

1.8.3 Exciton diffusion:

Ideally, all photoexcited excitons should reach a dissociation site. Since such a site may be at the other end of the semiconductor, their diffusion length should be at least equal to the layer thickness (for sufficient absorption), otherwise they recombine and photons are wasted. Exciton diffusion ranges in polymers and pigments are usually around 10 nm.

1.8.4 Charge separation:

Charge

separation

is

known

to

occur

at

organic

semiconductor/metal interfaces, at impurities such as oxygen or between materials with sufficiently different electron affinities (EA) and ionization potentials (IA). In the latter, one material can then act as electron acceptor (A) while the other keeps the positive charge and is referred to as electron donor (D). If the difference in IA and EA is not sufficient, the exciton may just hop onto the
26

material with the lower bandgap without splitting up its charges. Eventually it will recombine without contributing charges to the photocurrent.

1.8.5 Charge transport:

The transport of charges is affected by recombination during the journey to the electrodes, particularly if the same material serves as transport medium for both electrons and holes. Also, interaction with atoms or other charges may slow down the travel speed and thereby limit the current.

1.8.6 Charge collection:

In order to enter an electrode material with a relatively low workfunction (Al or Ca) the charges often have to overcome the potential barrier of a thin oxide layer. In addition, the metal may have formed a blocking contact with the semiconductor so that they cannot immediately reach the metal.

27

1.9 Characteristics of Organic Solar Cells: The following terms are often used to characterize solar cell. 1.9.1 Air Mass (AM):

A measure of how much atmosphere sunlight must travel through to reach the earths surface. This is denoted as AM(x), where x is the inverse of the cosine of the zenith angle of the sun. A typically value for solar cell measurements is AM1.5, which means that the sun is at an angle of about 48. Air mass describes the spectrum of radiation, but not its intensity. For solar cell purposes, the intensity is commonly fixed at 100W/cm2
(30)

1.9.2 Open-circuit Voltage (Voc):

The maximum possible voltage across a photovoltaic cell in sunlight when no current is flowing, termed as open circuit voltage. Open-circuit voltage of donor-acceptor bulk heterojunction photovoltaic is related directly to the energy difference between the HOMO level of the donor and the LUMO level of the acceptor material
(31)

1.9.3 Short-circuit Current (ISC):

This is the current that flows through an illuminated solar cell when there is no external resistance (i.e., when the electrodes are
28

simply connected or short-circuited). The short circuit current is the maximum current that a device is able to produce. Under an external load, the current will always be less than ISC.

1.9.4 Maximum Power-Point:

The maximum power point is the point (Impp, Vmpp) on the I-V curve where the maximum power is produced. Power (P) is the product of current and voltage (P=I.V) and is illustrated in the figure 1.13 as the area of the rectangle formed between a point on the I-V curve and the axes. The maximum power point is the point on the I-V curve where the area of the resulting rectangle is largest.

Figure 1.13: The short-circuit current (Isc), the OC voltage (Voc), the
voltage (Vmpp), and current (Impp) at maximum power point (Pmax).

29

1.9.5 Fill Factor (FF):

The fill factor is the ratio of the maximum power to the external short and open circuit values measure cell performance.
max (29)

.This is a key quantity used to

1.9.6 Power Conversion Efficiency (PCE):

Efficiency is an essential parameter for solar cells with respect to energy production and cost. The overall efficiency eff of a solar cell is calculated by the following formula:

Here, Pin is the sum over all wavelengths and is generally fixed at 100 W/cm2 when solar simulators are used. More detailed, at the AM1.5 conversion efficiency AM1.5 of the photovoltaic devices measured with a solar simulator is given by

Where, Pout = Output electrical power of the device under illumination. Pin = Light intensity incident on the device as measured by a calibrated reference cell. M = The spectral mismatch factor that accounts for deviations in the spectral output of the solar simulator with respect to the standard AM1.5 spectrum and deviations in the spectral response
30

of the device under measure with respect to that of the reference cell
(32)

1.9.7 Quantum Efficiency (QE): The efficiency of a device defined as a function of the energy or wavelength of the incident radiation. For a particular wavelength of the incident radiation it specifically relates the number of charge carriers collected to the number of photons shining on the device. Quantum efficiency can be reported in two ways: external quantum efficiency and internal quantum efficiency.

1.9.7.1 External Quantum Efficiency:

The External Quantum efficiency (EQE) is defined as the number of electrons flowing in the external circuit per photon incident on the photovoltaic cell
(33)

.This type of quantum efficiency includes

losses by reflection and transmission. External Quantum efficiency is also called IPCE (incident photon to current efficiency).

( )(

Where, h = lanks constant, C=velocity of light Pin= Incident photon flux at excitation wavelength . Usually, IPCE is given in percent and therefore
(34)

31

For a device based on exciton dissociation by charge transfer at a donor-acceptor interface, the external quantum efficiency (EQE) is governed by the following relation,

Here,

= Efficiency of photon absorption leading to generation of

an exciton.

1.9.7.2 Internal Quantum Efficiency:

It is defined as the ratio of the number of carriers collected at an electrode to the number of photons absorbed in the devices(33).This quantum efficiency factors out losses due to reflection and transmission of photons such that it consider process only involving absorbed photons. By accounting for transmission and reflection processes, external quantum efficiency (EQE) can be transformed into internal quantum efficiency (IQE).

1.10 Photoluminescence:

Emission of light upon irradiation is termed as photoluminescence

(35)

. When light of sufficient energy is incident on a material,

photons are absorbed and electronic excitations are created. Eventually, these excitations relax and the electrons return to the ground state. If radiative relaxation occurs, the emitted light is

32

called PL. This light can be collected and analyzed to yield a wealth of information about the photoexcited material. The PL spectrum provides the transition energies, which can be used to determine electronic energy levels. The PL intensity gives a measure of the relative rates of radiative and non-radiative recombination. Variation of the PL intensity with external parameters like temperature and applied voltage can be used to characterize further the underlying electronic states and bands
(36)

. PL phenomenon can be observed from figure 1.14.

Figure1.14 Photoinduced processes in the donoracceptor system. As

the photoinduced charge transfer (a) occurs on a much smaller timescale than photoluminescence (b) and recombination (c), the charge separated state is efficiently formed and metastable.

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