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Int. J. Materials and Product Technology, Vol. 34, No. 4, 2009

469

Optical properties engineering for Organic Solar Cells

Jean-Jacques Simon*, Ludovic Escoubas, Florent Monestier and Philippe Torchio

Aix-Marseille Université, IM2NP, CNRS, IM2NP UMR 6242 (Marseille – Toulon), Faculté des Sciences et Techniques, Campus de Saint-Jérôme, Avenue Escadrille Normandie Niemen – Service 231, F-13397 Marseille Cedex, France E-mail: jean-jacques.simon@univ-cezanne.fr E-mail: ludovic.escoubas@univ-cezanne.fr E-mail: florent.monestier@astron-fiamm-safety.com E-mail: philippe.torchio@univ-cezanne.fr *Corresponding author

François Flory

Directeur de Centrale Marseille Recherche et Technologies, and IM2NP UMR 6242, Ecole Centrale Marseille, Technopole de Chateau-Gombert, 38 rue Joliot Curie, 13451 Marseille Cedex 20, France E-mail: francois.flory@ec-marseille.fr

Abstract: Organic Solar Cells (OSC) have received increasing attention over the last few years for their potential technological applications as well as fundamental science. To increase the part of the incident light which is absorbed in the photoactive layer, optical properties of the cell are critical and should be optimised. In this paper, we review how photonics has stimulated researches and news experimental approaches to improve photovoltaic conversion in OSC. Solutions used to confine the light in the device are described and new architectures of organic solar cell are presented.

Keywords: solar cells; optics; organic materials.

Reference to this paper should be made as follows: Simon, J-J., Escoubas, L., Monestier, F., Torchio, P. and Flory, F. (2009) ‘Optical properties engineering for Organic Solar Cells’, Int. J. Materials and Product Technology, Vol. 34, No. 4, pp.469–487.

Biographical notes: Jean-Jacques Simon received his PhD at the University of Marseille in 1996 for a thesis on “Electrical activity of dislocations in silicon”. From 1997 to 2000, he worked as a process engineer for IBM Semiconductor at Corbeil-Essonnes, France. He joined the University Paul Cezanne of Marseille in 2000. Working at the IM2NP laboratory since 2007, his current research interests are photonics for organic solar cells and more generally microstructured optical components. He has authored more than 20 papers.

Copyright © 2009 Inderscience Enterprises Ltd.

  • 470 J-J. Simon et al. Ludovic Escoubas was graduated from Centrale Marseille (a French ‘Grande Ecole’ of Engineer), and received a PhD in Optics in 1997. He is now Professor at Paul Cezanne University (Marseille – France) and leader of the OPTO-PV Team (“Optoelectronics Components and Photovoltaics”) of IM2NP (CNRS Laboratory). His current research interests are micro and nano optical components and solar cells. He has authored more than 150 papers and communications and holds six patents. Florent Monestier was graduated from the Engineer School of Dijon (France) in 2004. After he did receive his PhD Degree (2008) from the University Paul Cezanne of Marseille, he joined the Astron-Fiamm-safety company as engineer. Philippe Torchio received his PhD in materials sciences in 1992. He has worked in the fields of semiconductor materials for photovoltaic applications, infrared absorption mapping, thin film deposition techniques, and optical coatings. He is now Senior Lecturer at the Paul Cézanne Aix-Marseille three University and member of the OPTO-PV Team (“Optoelectronics Components and Photovoltaics”) of IM2NP (CNRS Laboratory). His current research interests are photovoltaic cells, in particular organic solar cells, and micro or nano structured optical components. He has authored more than 100 papers and communications. François Flory received his PhD in 1978 and his ‘thèse d'Etat’ in 1985 in light scattering and in the relation between optical properties and the microstructure of thin films, respectively. He is now Professor in Optics at the Ecole Centrale de Marseille. He is editor of the book Thin Films for Optical Systems and of more than 150 papers and communications. He has been chairman or member of the scientific committee of more than 15 international conferences. His current research interest is now in the field of micro/nano photonics.

1

Introduction

Among the variety of renewable energies, photovoltaics is a proven technology. Today silicon is still the leading technology in the world market of photovoltaic solar cells, with power conversion efficiencies reaching 25% for mono-crystalline devices. Organic Solar Cells (OSC) have received increasing attention over the last few years. Indeed, the materials used in photovoltaic polymer domain offer many practical advantages over conventional photovoltaic materials such as silicon thanks to the solution processing techniques used to fabricate the cells (low cost, flexible and large scale applications). The power conversion efficiency of polymer-based solar cells has been significantly increased during the last years from 1% in 1986 (Tang, 1986) to 5% in 2005 (Xue et al., 2005) and more recently to 6% in 2007 (Kim et al., 2007). With such efficiencies, OSC will possibly be a competitive alternative way to inorganic solar cells in the near future. Generally, the different OSC are distinguished by the production technique (spin-coating, doctor blade or vacuum deposition techniques), by the photoactive materials used (polymer or small molecules) and by the device architecture (single layer, bilayer heterojunction or bulk heterojunction).

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The aim of this paper is to review how photonics has stimulated researches and news experimental approaches to improve photovoltaic conversion in OSC. After a short historic review of OSC, we will described, in the first part of this paper, the general architecture of OSC and the physical mechanisms leading to the generation and collection of charge carriers in such devices. Differences between OSC and conventional solar cells (silicon based) will be underlined. In a second part, we will focus on the optical optimisation of a standard organic solar cell (modulation of the electromagnetic field inside the device – implementation of periodic structures – realisation of tandem cells – use of plasmon properties). The third part will be devoted to news concepts and architectures of OSC. We will present recent efforts and promising routes to increase the interaction between light and OSC.

  • 2 Organic solar cells background

In 1959, the first investigation of an organic photovoltaic cell related to an anthracene single crystal was performed with a Schottky diode structure. The cell exhibited a photovoltage of 200 mV with an extremely low efficiency (Kallmann and Pope, 1959). Since then, many years of research have shown that the typical power conversion efficiency of PV devices based on single (or homojunction) organic materials will remain below 0.1%. The difficulty was to find an organic material presenting both best electrical properties (both for excitons, electrons and holes) and a sufficiently high optical absorption. A major breakthrough in the cell performance came in 1986 with the introduction of the bilayers device concept. In this device architecture an electron donor layer (D) and an electron acceptor (A) layer are stacked on top of each other in one cell, like a p-n junction in silicon solar cells. In the pioneering work of Tang (1986), a CuPc/perylene derivative bilayer system was sandwiched between In 2 O 3 and silver electrodes and reached a power conversion efficiency of around 1%. Due to the low exciton diffusion length, the efficiency of bilayer solar cells is limited by the charge generation which occurs only in a region of 10–20 nm around the Donor-Acceptor (D-A) interface. The revolutionary development in OSC came in the mid 1990s with the introduction of the bulk heterojunction devices (Yu and Heeger, 1995), where the donor and acceptor material are blended together. In such a nanoscale interpenetrated network, each exciton created could reach a dissociating site (interface D/A) within a distance lower than the exciton diffusion length. Nowadays, the bulk heterojunction is still the most promising concept for all-organic PV cells. Various combinations of donor and acceptor materials have been studied. Using regioregular poly (3-hexylthiophene) (RR-P3HT) as donor and 6,6-Phenyl C61-Butyric Acid Methyl ester (PCBM) as accceptor bulk heterojunction solar cells have been realised with external quantum efficiencies of around 75% and power conversion efficiencies up to 5% (Kim et al., 2006).

  • 3 Working principles of an organic solar cell

The structure of an OSC is depicted in Figure 1. As observed, the cell is illuminated through a transparent substrate. A conductive and transparent anode (usually a Indium Tin Oxide (ITO)) is deposited on the substrate and usually five layers are then deposited

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on top of this anode: a first interfacial layer (typically a film of PEDOT:PSS (poly(ethylene-dioxythiophene) doped with polystyrenesulfonic acid)), a photoactive layer, a second ultrathin interfacial layer (LiF (lithium fluoride) or BCP) and a thick cathode. The organic materials composing the photoactive layers are generally split into two groups: small molecules and conjugated polymers. Small molecules, which have a well-defined molecular weight, are deposited by low or high pressure vapour methods. To create interpenetrating D-A networks co-evaporation techniques can be applied. Polymers are usually processed from solution (spin-coating, doctor blading or screen-printing techniques (Shaheen et al., 2001).

Figure 1

Schematic of an Organic Solar Cell (see online version for colours)

472 J-J. Simon et al. on top of this anode: a first interfacial layer (typically a

There is a fundamental difference between solar cells based on inorganic or on organic semiconductors. In solar cells made from inorganic semiconductors, photons are directly converted at room temperature into free charge carriers (electrons and holes) which can be collected at their respective electrodes. In OSC, a photon absorption leads to the creation of a bound electron hole pair called exciton, which binding energies are ranging from 50 meV up to >1 eV (Gregg, 2003). Then excitons have to diffuse to be dissociated into free charges. This additional stage of excitons diffusion completely changes the scale of the physical phenomen involved in OSC. Indeed, in silicon photovoltaic technology, the electron diffusion length could reach the wafer thickness (>200 µm) even in polycrystalline silicon. In organic materials, both the exciton diffusion length and the charge carrier diffusion lengths are in submicronic range (10–20 nm for excitons and 100–200 nm for charge carriers). The most visible consequence of such low values is the design of the organic photovoltaic devices where the active layer thicknesses do not exceed 200 nm. In addition, the control of the morphology of each layer at the nanometer scale strongly impact the performance of OSC. Before going more into the details, we recall here the four steps of the photovoltaic conversion process in OSC (see Figure 2):

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Figure 2

Energetic diagram and photovoltaic conversion process in OSC (see online version for colours)

Optical properties engineering for Organic Solar Cells 473 Figure 2 Energetic diagram and photovoltaic conversi on
  • 3.1 Photon absorption (photon absorption efficiency: η A )

Upon absorption of a photon having an energy larger than the gap, an electron is promoted from the Highest Occupied Molecular Orbital (HOMO) band to the Lowest Unoccupied Molecular Orbital (LUMO) band of the donor material. The majority of organic materials have band gaps higher than 2 eV which limits to less than 30% the possible harvesting of solar photons when a gap of 1.1 eV (silicon) makes possible to absorb 77% of solar radiations. Moreover, due to low charge carrier mobilities, the active layer thickness should be restricted to around 150 nm to avoid serie resistances. Fortunately, absorption coefficient are high in organic materials (exceeding 10 5 cm 1 ) and make possible to absorb the main part of the incident light even with a thicknesses of around 100 nm. Thicknesses of the films are not the bottleneck.

  • 3.2 Exciton diffusion

The strong local electrical field at a D-A material interface will be used to dissociate excitons. For efficient dissociation of excitons, the distance between the photon absorption and the first interface should be lower than the exciton diffusion length (between 10 nm and 30 nm).

  • 3.3 Exciton dissociation or charge separation (exciton dissociation efficiency: η D )

When an exciton reaches the interface between donor and acceptor materials, the charge separation takes place in an ultrafast timescale of about 45 femtoseconds (Brabec et al., 2001). However, a necessary condition for efficient dissociation of the created excitons is that the difference between the LUMO of the donor and the acceptor is higher than the exciton binding energy. If this is the case, electrons are transferred to the acceptor. Up to now, in conjugated polymer based OSC the most efficient electron acceptors found are

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C60 based fullerenes. Because the separation is faster than any other competing process, its efficiency is about 100%.

  • 3.4 Charge transport (charge carrier collection efficiency: η CC )

The separated charges then need to diffuse to the respective device electrodes, holes to the anode and electrons to the cathode to provide voltage. In conjugated polymer, transport charge carriers is done by successive jumps (hopping) form a located state to another, which is a notable difference with the inorganic semiconductors, where the conduction electrons move freely through delocalised states. Mobilities in organic materials are low and could also be reduced by traps. Values are typically 10 4 cm 2 /V.s. but higher mobilities have been reported in pentacene (Unni et al., 2004; Jurchescu et al., 2004). In the following, we will focus on optical properties engineering in OSC. More details on the other properties of OSC are available in many recent reviews:

  • 4 Optical optimisation of an organic solar cell

The basic idea developed in this paragraph is to increase the part of the incident light which is absorbed in the photoactive layer. An example of the spectral redistribution of the incoming light (on reflection and layer absorption) for a standard bulk heterojunction solar cells (pentacene:

PTCDI-C13H27 blend) is shown in Figure 3. If most of the incoming light is absorbed in the blend in the 400–700 nm range, average reflection is about 10%, ITO absorption is about 15% while PEDOT absorbs mainly in the blue range (4%). Although a remarkably high external quantum yield measured in this device (83%), the best power conversion efficiency reported for this couple of materials does not exceed 2% (Pandey et al., 2006).

Figure 3

Electromagnetic field distribution in OSC (see online version for colours)

474 J-J. Simon et al. C60 based fullerenes. Because the separation is faster than any other

The first approach to improve the performance of the cell is to increase the thickness of the absorbing layer. However, this thickness is generally restricted (<150 nm) by the

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limited charge carrier mobility in conjugated polymers (highly efficient devices with thickness around 200–250 nm have been recently demonstrated (Irwin et al., 2008)). Thus, to overcome this problem and from the optical point of view the following solutions can be considered:

optimisation of the electromagnetic field distribution inside an OSC

fabrication of tandem cells

implementation of periodic structures (such as gratings or photonic crystals) in the thin layers stacking

investigation of plasmons effects for increasing absorption in OSC.

  • 4.1 Optimisation of the electromagnetic field distribution

A solar cell can be represented by stacked thin films surrounded by a semi infinite substrate and a semi infinite transparent medium (Figure 3). Each layer ‘i’ is defined by its thickness d i and by its refractive index n i and its extinction coefficient k i as a function of wavelength λ. In such a device, when layer thicknesses are thin compared to the coherence of the incident light, interference effects are not neglected and the one dimensional transfer matrix formalism (Berning and Berning, 1963) has to be applied to modelise the distribution of the electromagnetic field inside the solar cell (Pettersson et al., 1999). An example of the distribution of the squared modulus of the electromagnetic field IEI², in the depth of the device and for wavelengths between 300–600 nm, is given in Figure 4. To go further into details and to link the optical properties to the electrical properties in OSC, the key equation is the following one:

(,

Qz

1 ε n 2 2 E λα µ 0 i ( z ) ) = n
1
ε
n
2
2
E
λα µ
0
i
(
z
)
)
=
n
Ez
()
=
α
I
i
solarlight
E
2
0
n
0
0

(1)

where Q is the local energy dissipated in the material, ε 0 is the permittivity of vacuum and µ 0 is the permeability of vacuum, α is the absorption coefficient, n 0 is the real part of the complex refractive index of the glass substrate, and I solar light is the polychromatic incoming light with standard AM1.5 distribution. Indeed, from equation 1 and by taking into account values (η A , η D and η CC ), the generation rate of free carriers G(z) and the short current density J sc can be computed (Peumans et al., 2003) and used to predict the organic solar cell efficiency. Thus, a large number of recent papers concerns the comparison between experimental results and optical modelisation of OSC (Sievers et al., 2006; Monestier et al., 2007b; Sylvester-Hvid et al., 2007). For example, it has been shown that the dependency with the active layer thickness of the short circuit current density of OSC based on blend heterojunction (Figure 5) follows a rather complicated behaviour (Moulé and Meerholz, 2007; Hoppe and Sariciftci, 2007; Monestier et al., 2007b). Furthermore, based on the electromagnetic field optimisation, Monestier et al. (2007a) has developed an automatic software for optimising the design of OSC. As regards organic tandem cells, this software is set to find simultaneously optimal thickness of each layer and to balance the photocurrent in the two active regions. In summary, optical modelling is essential to understand the behaviour of OSC devices consisting of multilayer structures.

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Figure 4 3D representation of the electromagnetic field distribution vs. incident wavelength inside an organic solar
Figure 4
3D representation of the electromagnetic field distribution vs. incident wavelength
inside an organic solar cell (see online version for colours)
Figure 5
Comparison of computed short circuit current density (solid line) with experimental
data (circles) as a function of blend thickness
476 J-J. Simon et al. Figure 4 3D representation of the electromagnetic field distribution vs. incident
  • 4.2 Realisation of tandem cells

Because of the narrow absorption spectra of most organic materials used in solar cells, tandem structures must be considered. The idea of a tandem cell is to achieve a better absorption efficiency by using materials having different band gap. Then one material collect the higher energetic photons and the other, one with a lower band gap than the first one, absorbs photons with lower energy. In a tandem cell, two OSC are deposited on top of each other and can be connected in serie or in parallel. In serial connection, the intermediate electrical contact layer is of a major importance:

it should acts as a recombination centre to prevent cell charging

it should be as transparent as possible

it should act as a optical spacer to confine the energy in the two active layers. As regards the fabrication of polymer tandem cells, an other criterium is required:

the intermediate layer has to protect the bottom cell during the deposition of the top cell (preventing dissolution or damaging the bottom cell specially when similar solvents are used). This intermediate layer is regarded as a bottleneck for the development of polymer

Optical properties engineering for Organic Solar Cells 477

tandem cells. For more details please refer to the review of organic tandem cells which has been recently published by Hadipour et al. (2008). The first significant power conversion efficiency of an organic tandem cell (2.5 %) has been described by Yakimov and Forrest (2002). The two cells were connected by a silver layer. In the work of Xue et al. (2004) related to tandem cells based on evaporated layers of small molecules (CuPc and C60), a power conversion efficiency higher than 5% is achieved using Ag nanoclusters with a typical thickness 0.5 nm instead of a very thin Ag interlayer as used before for the separating layer. The role of the Ag nanoclusters is not yet clearly understood, in addition to recombination centres, silver particles can also serve as scattering centres for incident light and can also excite plasmons as it will be shown in the part three of this paper. Then, various concepts of intermediate layer were successively introduced in order to allow the fabrication of polymer tandem cells:

by Kawano et al. (2006) with ITO deposited by sputtering

by Hadipour et al. (2006) with a composite layer of Al, Au, Lif and PEDOT:PSS

by Gilot et al. (2007a) with ZnO nanoparticles deposited by spin coating and covered by a neutral PEDOT layer.

Finally, with a power conversion of 6.7% the recent work of Kim et al. (2007) is the best power conversion efficiency reported until now and not only for organic tandem solar cells but for all OSC. To reach this value, the authors have used a highly transparent sol-gel processed titanium oxide (TiO x ) as intermediate layer and a second TiO x layer between the top cell and the Al electrode (Figure 6). As explained by the authors, this second layer acts as an optical spacer that redistributes the light intensity to optimise the efficiency of the back cell. This work confirms that inserting a transparent electron transporting layer between the active layer and the Al top electrode allows us to confine the electromagnetic field inside the active layer. The same effect has also been demonstrated by Gilot et al. (2007b) with a ZnO layer as the optical spacer.

Figure 6

Tandem polymer solar cell as describe in by Kim et al. (2007) (see online version for colours)

Optical properties engineering for Organic Solar Cells 477 tandem cells. For more details please refer to

It is important to note that more than 200 individual tandem cells were necessary, as reported by the authors, to optimise the fabrication procedure and device architecture

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(optimising and balancing the current in each subcell), proving that the optical modelisations described previously are essential. In summary, the organic tandem cell research has developed during the last five years with a scientific interest triggered by a rapid increase in power conversion efficiencies. This was achieved by the introduction of new materials, but mainly by the improvement of technical processes (sol-gel technique) and the improvement of the understanding of the optical properties of the multilayer structure. To go further, the knowledge coming from optical interference coatings (generally inorganic) may allow the development of new concepts.

  • 4.3 Implementation of periodic structures in the multilayer stack

Periodic structures for light trapping have been used extensively to enhance absorption in silicon solar cells in addition to standard anti-reflection coatings. Silicon wafer random texturing is usually achieved in commercial solar cells using anisotropic etching of the silicon network. More complex techniques, like reactive ion etching, have been performed to obtain high-efficiency structures based on pyramids (Zechner et al., 1998). Most of the above structures usually have feature sizes larger than 10 µm and are efficient because they use the geometric optics phenomenon of ray trapping. To reach un-polarised reflectances as low as 1–4% submicrometric structures are needed (Hava and Auslender, 2000). In OSC the context is different: reflectivity losses at the air-device interface are lower than in silicon, around 4% for an air-glass interface instead of 30% for an air-silicon interface, but the absorption of organic solar cell photoactive layers is too weak as explained above (mainly the high organic materials band-gap). Thus, the challenge in OSC is to implement periodic structures inside the multilayer stack to confine the incident light in the active layer (see Figure 7). Optical simulations and realisation of diffractive optical structures in OSC have been first investigated by Niggemann (2004). Their work is base on two concepts described in Figure 8: diffraction gratings (a) and buried nano-electrodes (b). The Rigorous Coupled Wave Analysis (RCWA) method was used in both architectures. In case (a), the sinusoidal grating leads to a resonant coupling of the light into the active polymer film ((MDMO-PPV:PCBM) blend – 200 nm thick) and the substrate acts as a light-guide for propagating diffraction orders. The diffraction grating has been realised by embossing technique (period of 720 nm and

a depth of 190 nm). In case (b) the acrylic substrate is nanostructured to enhance the charge carriers collection at the electrodes. Dimensions of the nanostructure are a period of the lamellae of 720 nm, a depth of approximately 400 nm and a width of the cavities of 400 nm. Although some difficulties to correlate computations and initial experimental results, the potential of diffractive optical structures for OSC has been evaluated for the first time by this researchers team. More recently, Yang et al. (2007) has evaluated the short-circuit photocurrent given by an OSC containing nanograting heterojunctions using a two-dimensional analytic exciton transport theory. In this work the optical properties of the nanogratings are neglected (homogeneous theory) because the authors assumed that the dimension of the gratings (period of 100 nm and height ranging between 10 nm and

  • 140 nm) are much smaller than the incident wavelength (300–800 nm).

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Figure 7 Diffractive optical structures in OSC (diffraction gratings (a) and buried nano-electrodes (b)) as describe
Figure 7
Diffractive optical structures in OSC (diffraction gratings (a) and buried
nano-electrodes (b)) as describe by Yang et al. (2007) (see online version for colours)
Figure 8
Distribution of the incoming energy in a bulk heterojunction solar cell
ITO/(pentacene/PTCDI-C13H27 blend)/BCP/Al. (The thin BCP layer is
included but not represented)
Optical properties engineering for Organic Solar Cells 479 Figure 7 Diffractive optical structures in OSC (diffraction

Still to increase the interaction of the light with the photoactive layer, an original study of nanometric periodic patterning for enhancement of OSC power efficiency has been reported by Cocoyer et al. (2006). As illustrated in Figure 9, a nanostructured azopolymer layer is used as a substrate in a classical CuPc/C60 bilayer organic solar cell (ITO/PEDOT/CuPc/C60/BCP/Ag). Sinusoidal periodic structures are realised in one step using optical interferences. A mass transport process occurs in azopolymer films when illuminated. According to the grating formula, new absorption bands (which depends on the grating period) appear in the external quantum efficiency spectra leading to an enhancement of the short-circuit photocurrent (Jsc) of about 15%. Indeed 2D gratings can increase the interaction of the light with the photoactive layers in OSC by coupling a part of the solar spectrum into a quasi-guided mode. This is clearly one of the solution to increase the overlapping between the absorption range of OSC and the solar spectrum. Before closing this part, we would like to mention a preliminary study of Escarre et al. (2005) devoted to the realisation of random roughness surfaces on plastic substrates by means of hot embossing processes. Different random roughnesses (nanometer and micrometer sizes) have been transferred on poly(methylmethacrylate) (PMMA) using two kind of master (commonly available frosted glass and commercial transparent conductive oxide). After stamping, the PMMA rough surfaces have been optically characterised by measuring the transmitted and reflected scattered light (red-diode laser source (λ = 633 nm)). With a roughness RMS value around 2.6 µm, the PPMA layer embossed with a frosted glass exhibits the best optical behaviour (much closer to an ideal diffuser). Beyond the results, this work demonstrates that a low cost technique

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(hot embossing) with available and cheap masters (frosted glass) can be used to produce random textures on plastic surfaces. This can be of a great interest to enhance the absorption an OSC, especially in the near infra-red domain.

Figure 9

Schematic of an organic solar cell with a nanostructured substrate as describe by Cocoyer et al. (2006) (see online version for colours)

480 J-J. Simon et al. (hot embossing) with available and cheap masters (frosted glass) can be
  • 4.4 Plasmons for increasing absorption in OSC

An optically generated oscillation of free electrons that takes place along a metal/dielectric interface is a surface plasmon. By tuning the excitation light, a resonance occurs when the incident photon frequencies match the collective oscillations of the conduction electrons of the metallic particles. In photonics, this field of interest is known as plasmonics. Among a wide range of applications, these surface plasmons properties can be used in photovoltaic domain in order to improve performances of solar cells. Noble metal particles such as gold or silver can exhibit an enhanced absorption in the visible range. Thin film amorphous silicon solar cells were manufactured by Derkacs et al. (2006) in which gold nanoparticles were used to engineer the transmission and spatial distribution of the electromagnetic fields in visible wavelengths inside a-Si:H layer, resulting in an increase of 8.1% in short-circuit current density and 8.3% in energy conversion efficiency compared to values achieved in reference devices without gold particles. Pillai et al. (2007) found that surface plasmons can increase response of silicon cells over the visible as well as near-infrared spectra. They reported a significant enhancement of the absorption for both thin-film and wafer-based crystalline silicon structures including silver nanoparticles. This light trapping approach also based on the effect of scattering by particles in silicon devices allows clearly an amplication of the interaction between light and material. This work was initiated by Schaadt et al. (2005). Similar studies were carried out with organic materials to enhance light absorption, subsequently leading to an increase in the amount of excitons. In the systems ITO/metal-clusters/CuPc/In, it was shown by Stenzel et al. (1995) that the incorporation of copper or gold increases the photocurrent by a factor of more than 2. This work was also performed with ITO/silver-clusters/ZnPc/Ag components by Westphalen et al. (2000). A schematic of such devices using surface plasmons effect is given in Figure 10. Optical properties of silver nanoparticles used in tandem thin-film OSC were investigated by Rand et al. (2007a, 2007b). The multiplayer stack consists in a serie connection of two

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D-A heterojonctions including a very thin metallic nanocluster layer separating each subcell. It was shown an optical-field enhancement due to plasmon generation on the ultra-thin cluster surfaces which involved higher efficiencies.

Figure 10 Schematic of the simple structure with the intermediate metallic clusters layer

Optical properties engineering for Organic Solar Cells 481 D-A heterojonctions including a very thin metallic nanocluster
  • 5 New organic solar cell architectures for the enhancement of light harvesting

At the same time, apart the development of new photovoltaic organic materials, many studies concern new architectures of organic solar cell which are alternative to the typical thin film structures described in the first part of this paper. This research area can be illustrated by four examples of architectures in which new optical properties of OSC are demonstrated:

an organic solar cell manufactured on the model of an optical fibre (Liu et al., 2007) a folded reflective tandem organic solar cell (Tvingstedt et al., 2007) an OSC without ITO (Tvingstedt and Inganas, 2007) a luminescent concentrator coupled to an organic solar cell (Koeppe 2007).

  • 5.1 Optical fibre based architecture

In this work, Caroll and co-workers have investigated the possibility to convert photons into electrons using a modified standard multimode optical fibre. As shown in Figure 11, the basic idea is to replace the conventional hard polymer cladding by a photovoltaic material layer (P3HT/PCBM). In such a structure, electrons are collected by an ITO layer inserted between the fibre core and the active layer while the holes are collected by an aluminium layer recovering the fibre. The working principle is as following: a part of the incident light is coupled into the fibre (illumination of the cleaved face at normal angle of incidence) and is attenuated during propagation because of the absorption in the active layer. High current densities near 28 mA/cm 2 are obtained, proving that the internal conversion efficiency is very high in such architecture. Conversion efficiency of 1.1% is achieved after optimisation of the fibre diameter.

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Figure 11 Optical fibre based architecture for OSC as describe by Liu et al. (2007) (see online version for colours)

482 J-J. Simon et al. Figure 11 Optical fibre based architecture for OSC as describe by
  • 5.2 A folded reflective tandem organic solar cell

An original OSC architecture has been developed by Swedish researchers (Tvingstedt et al., 2007), as shown in Figure 12 the cell exhibits a V shape geometry and combines two different cells realised on each face of the V structure. The two cells are based on alternating copolymers of fluorene (APFO3 and APFO-Green9) as donors and PCBM as acceptor. The both materials are first deposited on a flat substrate which is then folded. The first advantage is the broad spectra of absorption of this structure: the APFO-Green9 absorbs mainly in the red range while the APFO3 absorbs until 850 nm. In addition, the folded structures cause light trapping at high angles. And finally, this architecture allows to use tandem or multiple bandgap solar cells in optical and electrical series or parallel connection. Added to the power conversion efficiencies demonstrated in this work (between 3% and 4%), process allows a large scale production of folded reflective cells by roll to roll inkjet printing.

Figure 12

Folded reflective tandem organic solar cell as describe by Tvingstedt et al. (2007) (see online version for colours)

482 J-J. Simon et al. Figure 11 Optical fibre based architecture for OSC as describe by
  • 5.3 An organic solar cells without ITO

The same Swedish group has also developed a very interesting method to eliminate the ITO layer from the classical OSC architecture. Because the amount of Indium is limited on the earth, the idea of the authors is to replace ITO layer by metallic micro grids (Figure 13). It could be an alternative to new transparent conductive oxydes (TCO) or to

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more complex stacks like a thin metallic layer embedded between two transparent layers. Metallic grids are already used to realised the electrode at the front side of silicon solar cells. The thickness of the silver grips for OSC is much smaller than in the case of silicon solar cells (around 100 nm instead of more than 10 µm) but the working principle is the same: dimensions of the grids are optimised to reach the conductivity needed (around 2 × 10 5 S.cm 1 ) and the period of the structure is calculated to minimise the shadow effect of the metallic grids. The power conversion efficiency (1%) of this free ITO solar cell is found to be better than the ITO based OSC (0.83%). This remarkable result is obtained by using a new high conductive layer: a PEDOT:PSS with diethylene glycol (DEG) for which conductivity is 4000 times higher than conventional PEDOT:PSS. However, if the concept of such architecture without expensive ITO is demonstrated, the process to realise the grids remains complex with a fluidic deposition method exploiting PDMS stamps. For manufacturing, a cheaper grids deposition technique should be developed.

Figure 13 Architecture of an OSC without ITO as describe by Tvingstedt and Inganas (2007) (see online version for colours)

Optical properties engineering for Organic Solar Cells 483 more complex stacks like a thin metallic layer
  • 5.4 A luminescent concentrator coupled to an organic solar cell

As underlined before, an important feature of OSC is the limited spectral range of absorption of OSC. To overcome this limitation, low energy band gap materials are intensively investigated. Koeppe et al. (2007) have chosen another way: authors report the application of luminescent concentrators on OSC. As in the concept of ‘antenna systems’, in this work, optical absorption and charge transport are dissociated. Indeed, as shown on Figure 14 the light is absorbed in a luminescent concentrator made of polymethyl methacrylate plate doped with red dye. Such dyes absorb in the 550–750 nm range and are luminescent in the 400–600 nm range. The luminescent light is collected by two OSC based on a ZnPC:C60 blend and fixed onto the respective sides of the concentrator plate which acts as a waveguide. In the future, the most important application of this architecture for an OSC mass production could be to used the concentrator as a substrate.

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Figure 14 A luminescent concentrator coupled to an OSC as describe by Koeppe et al. (2007) (see online version for colours)

484 J-J. Simon et al. Figure 14 A luminescent concentrator coupled to an OSC as describe

6

Conclusion

Recently, OSC have broken the 6.5% power conversion efficiency barrier. In this paper we have reviewed how photonics has stimulated researches and news experimental approaches to improve photovoltaic conversion in OSC. If it seems to be sure that new materials are needed to push the efficiencies into the 10% range, developing new optical concepts (including photonic crystal for example) might be one promising way for OSC development.

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