Proceedings of the ASME 2010 International Mechanical Engineering Congress & Exposition IMECE2010 November 12-18, 2010, Vancouver,

British Columbia, Canada

IMECE2010-37393
ANALYSIS AND CHARACTERIZATION OF SURFACE PLASMON ENHANCEMENT OF LIGHT ABSORPTION IN ORGANIC SOLAR CELLS BY THE TRANSFER MATRIX METHOD
Francisco V. Ramrez Departamento de Ingeniera Mecnica Universidad de Santiago de Chile, Alameda 3363 Estacin Central, Santiago, Chile francisco.ramirezcu@usach.cl Amador M. Guzmn Departamento de Ingeniera Mecnica Universidad de Santiago de Chile, Alameda 3363 Estacin Central, Santiago, Chile amador.guzman@usach.cl

ABSTRACT Surface plasmons enhanced light absorption in organic solar cells based on a photoactive poly(2-methoxyl-5-(2-ethylhexyloxy)-1.4-phenylenevinylene):(6.6)-phenyl-C61-butyricacid-methylester (MEH-PPV:PCBM), is studied by a computational model based on the transfer matrix method (TMM). Two physical situation with and without the bulk heterojunction film are considered and modeled on a 2D array of silver nanoparticles with a diameter of 40 nm embedded in a 50-nm-thick layer. The numerical simulation results that include optical properties in the wave length range of 350 and 750 nm, present qualitative and quantitative good agreement with previous results obtained by Duche et al (2009) in both conditions. Optical absorption results for incident light at an oblique angle of incidence are also obtained, with the purpose of determining the effect of the angle of incidence on the absorption properties. INTRODUCTION Photovoltaic, is one ofthe most effective technologies to produce energy in a sustainable way. However, the low efficiency and high cost of the photovoltaic modules are the main limitations to make solar energy as an alternative to fossil fuel. One proposed approach for low-cost photovoltaic energy is to reduce the thickness of the active material. Such thin film technology also offers, among other improvements, lower bulk recombination, larger areas compared with silicon wafers, and higher open circuit voltages. However, thin film solar cells have

reported lower efficiencies compared to wafer-based silicon cells since the relative poor light absorption (Green, 2003) In order to improve optical absorption, light trapping techniques are currently developed. One proposed way to light absorption enhancement, since optical absorption depends on the optical path length and the electric field intensity, is to increase the local field intensity via Localized Surface Plasmonsusing metallic nanoparticles. Plasmons are collective oscillations of the conduction band electrons excited by incident electromagnetic waves (Kittel, 2005). These modes are supported in noble metals as cooper, gold and silver. When plasmons are in confined geometries, such as small metal particles, they are called Localized Surface Plasmons (LSP). Upon excitation of light, LSP leads to an accumulation of polarization charges in the particle surface which acts as a restoring force that can reach a resonance at a particular frequency, called Surface Plasmon Resonance (SPR). As a consequence, the electromagnetic field intensity is increased around the close vicinity of the particle. (Pillai, 2007) An interesting attribute of LSP is that SPR is related to the particle size, shape, and optical properties of the particle and the surrounding medium (Kreibig & Vollmer, 1995), which allows the possibility of tuning the resonance frequency in a desirable way. A variety of approaches for increasing optical absorption in photovoltaic cells based on excitation of Surface Plasmons has been explored, either to crystalline silicon wafer(Pillai, 1 Copyright 2010 by ASME

Catchpole, Trupke, & Green, 2007), thin film silicon (Pillai, Catchpole, Trupke, & Green, 2007; Akimov, Ostrikov, & Li, 2009), and organic solar cells devices (Duche, et al., 2009; Rand, Peumans, & Forrest, 2004). However, there are few investigations that use either analytical solutions or numerical simulations to understand the Surface Plasmonsphenomena. Hu et al. (2008), used an analytical model based on an extended Mie Scattering Theory to analyze the electromagnetic field distribution of a single silver particle surrounded by silicon, without particle-particle interactions. Similar analysis were carried out by Derkacs et al. (2006), for a single gold particle at a fixed frequency, but using finite-element electromagnetic simulation. Rand et al. (2004), analyzed the absorption and intensity enhancement using two-dimensional finite-element simulations, therefore considering a one-dimensional array of silver cylinders instead of spheres. Duche et al. (2009) studied the absorption and electromagnetic field power density distributions of an array of silver nanoparticles embedded in an organic material using FDTD simulations. In this paper, we present a different approach based on simulations using the transfer matrix method (TMM) for characterizing the optical absorption enhancement in organic solar cells. The TMM scheme has presented good performance for obtaining the optical absorption in metal particles arrays, where the dielectric constant has excursions from large to very low values at nearby positions (Pendry, 1994). In order to validate the computational code used in this investigation, we first analyze two specific problems studied by Duche et al.(2009) considering incident light at normal incidence; then, we analyze the effect of the angle of incidence on the absorption properties. TRANSFER MATRIX METHOD The TMM is a finite difference frequency domain method, where the electric ( ) and magnetic ( ) fields on one side of a unit cell are related to those on the end by a transfer matrix ( ). This transfer matrix arises from a discrete approximation of the frequency domain Maxwell equations on a simple cubic lattice (Pendry, 1996), which leads to the following expression:

To perform the simulations, we take a central differences approach in contrast with the forward-backward approximation used in the original Pendrys code (Pendry, 1995; 1996). This approach is based on a Yee cell, used in the FDTD method (Taflove & Hagness, 2000), where every electric field component is surrounded by four circulating magnetic field components and vice versa (Figure 1), in order to have more accurate results without any additional memory requirements and/or processing time.

Figure 1 Elementary Yee cell

NUMERICAL MODEL In our analysis, we considerthe same problem studied by Duche et al (2009), a two dimensional periodic array of silver nanospheres with 40nm diameter (Figure 2). The structurehas a squared lattice with period of 75nm and is located in the base of a 50nm layer which represents the surrounding medium. The direction of the incident light is given by the zenith and azimuthal angles (Figure 2c). (a)

(b)
1 50nm 40nm

(c)

Where is the transfer matrix at a given frequency and is related to both, the dielectric and permeability constants. Usually, both, the dielectric constant ( ) and relative permeability ( ) dispersions are given in terms of frequency (Palik, 1998), so no Fourier transformation is needed. The reflection and transmission coefficients of a structure can then be obtained through a unitary transformation of the transfer matrix based on a plane wave basis in the reference medium (Pendry, 1994).

75nm Figure 2 Model of a 2D array of silver nanospheres: (a) Schematic representation; (b) Dimensions; (c) Incident light direction given in terms of zenith ( ), and azimuthal ( ), angles

The simulations are performed considering, as the surrounding medium, first air and thenan organic solar cell material MEH2 Copyright 2010 by ASME

PPV:PCBM. The dispersion curves of the complex refractive indices of MEH-PPV:PCBM are presented in the Figure 3. These values are the same used by Duche et al. and were obtained from experimental ellipsometric measurements performed by SOPRA S.A. company. The energy gap of the considered bulk heterojunction was found to be equal to 2.16 eV ( =575 nm).

Where is the dielectric constant of the surrounding medium and and are respectively, the real part and the imaginary part of the dielectric constant of the metal. When or are small, which is typically true for silver, equation 3 can be simplified to:
4

Considering the dielectric constant of both, the bulk heterojunction film (MEH-PPV:PCBM) and silver, equation 4 is satisfied at 357 nm, which is very close to the observed absorptance peak value in Figure 4.

Figure 3 Dispersion curves of the complex refractive indices of MEHPPV:PCBM used in the simulations performed by Duche et al. (2009).

To obtain the optical constants of silver Duche et al.(2009) used a Drude model given by: 365
2 Figure 4 Calculated values of reflectance (R), transmittance (T) and absorptance (A) versus wavelength for a 2D array of silver nanospheres placed in air

This model was then used as a fit law for the complex dielectric constant of silver. The results for the constants were: , , In our calculations, we used a spatial grid of , . The optical absorption measurements A were obtained at every frequency by an energy balance given by , where and are the frequency dependent reflectance and transmittance of the structure, respectively. The wavelength range is from 350 to 750 nm. RESULTS AND DISCUSSIONS TMM was used to determinate the reflectance, transmittance and absorptance for a two dimensional array of silver nanospheres placed in air, considering light at normal incidence (Figure 4). As Figure 4 shows, a peak is reached by the absorptance at a wavelength of 365 nm due surface plasmon excitation. Considering that the diameter of the spheres is small compared to the wavelengths of the incident waves, we can predict the resonance wavelength minimizing the following expression(Kreibig & Vollmer, 1995):
3

In order to evaluate LSP absorption enhancement in the bulk heterojunction film, optical absorption curves for light at normal incidence were obtain by TMM for the two dimensional array of silver nanospheres placed in air, embedded in MEHPPV:PCBM, and for the MEH-PPV:PCBM bulk heterojunction alone(Figure 5).

455
Figure 5 Optical absorption curves for: silver nanoparticles placed in air, MEH-PPV:PCBM alone, and the silver nanospheres array embedded in MEH-PPV:PCBM

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The results show a clearly absorption enhancement along all the spectral range considered in the analysis. The most interesting effect occurs at the wavelength range between 550nm and 750nm, where both, the MEH-PPV:PCBM and the silver nanoparticles array in air, presented low optical absorption. The absorption enhancement in the wavelength range from 350nm to 550nm, could be attributed to light absorption inside the metal, since the absorptance for the silver nanoparticles in air at this wavelength range (figure 4), is not negligible. On the other hand, the SPR for the metallic array embedded in the bulk heterojunction film is redshifted by 95 nm to 455 nm, in comparison with the resonance reached by the silver nanoparticles array placed in air, which is in accordance with the equation 4(Kreibig & Vollmer, 1995). In order to evaluate the effects of the angle of incidence on the absorption curve, we calculate the absorptance on the silver nanoparticle array embedded in MEH-PPV:PCBM for light incident with and for both, TE and TM polarized light. The results were compared with the absorption curve for light at normal incidence (figure 6).

silver nanospheres placed in air and embedded in MEHPPV:PCBM, presents good agreements with previous obtained using FDTD method by Duche et al. (2009). In comparison with the FDTD method, TMM has proven to be more suitable to characterize surface plasmons phenomena, since the modeling structure is highly resonant and time domain schemes take a huge number of iterations in time in order to reach the stability of the electromagnetic field. On the other hand, FDTD method accuracy requires more fine grids than those required by using the TMM. However, since TMM is based in harmonic modes, transient behavior of electromagnetic field inside the structure cannot be obtained. Absorption curves by incident light at an oblique angle of incidence in a silver nanoparticles array embedded in MEHPPV:PCBM are also obtained. Compared results with light at normal incidence, shows that surface plasmons excitation by a TE polarized light at any zenith angle presents similar absorption levels, since the electric field remains in the same direction respect to the normal incidence. Nevertheless, surface plasmons exited by TM polarized light produce higher absorption levels. SPR for TE polarized light is slightly blueshifted, in comparison with resonance at normal incidence, while for TM polarization SPR remains the same, This last results shows a slightly dependence between SPR and the magnetic field It has been proven that localized surface plasmons excitation increase the absorption levels in the organic solar cell proposed. However as we notice, for some wavelength ranges the absorptance by the silver nanoparticles is not negligible. The light absorption inside the silver nanoparticles do not contribute to photo-generated current, therefore it would be desirable to obtain electromagnetic field distributions inside the structure in order to separate the absorption of the nanoparticles from the bulk heterojunction structure absorption levels, by means of TMM approaches.

Figure 6 Absorption curves for an array of silver nanospheres embedded in MEH-PPV:PCBM for both, TE and TM polarized light at , and for light at normal incidence

ACKNOWLEDGMENTS Financial support provided by the Chilean Fondo Nacional de Ciencia y Tecnologa FONDECYT through projects 1100238, the Mechanical Engineering Department of Universidad de Santiago de Chile, and Dicyt, through the research fund 209124B is greatly acknowledged. REFERENCES A Program for Calculating Photonic Band Structures and Transmission Coefficients of Complex Structures 1995 Comp. Phys. Com., (85) 306-322 Calculating Photonic Band Structure 1996 J. Phys.: Condens. Matter,(8)10851108 Computational Electrodynamics: The Finite-Diferences TimeDomain Method 200 0Norwood, MA Artech House

As expected, for TE polarized light at the absorption curve remains very close compared with those at normal incidence. This is because Surface Plasmons are excited by the electric fields, and for a TE polarized wave the electric field direction is the same at any value of with .TM polarized wave however, presents higher absorption levels compared with those at normal incidence. SPR is slightly blueshifted for TE polarized light, in comparison with light at normal incidence, while for the TM polarization the resonance is reached at the same frequency. SUMMARY AND FINAL REMARKS In summary, we have studied the surface plasmons enhancement of light absorption in organic solar cells by means of a TMM based computational code. Our calculations based on transmittance, reflectance and absorptance levels for an array of

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