Supporting information for

Thermally evaporated Ag nanoparticle films for

plasmonic enhancement in organic solar cells: effects of
particle geometry
Gholamhosain Haidari*,1, Morteza Hajimahmoodzadeh1,2, Hamid Reza Fallah1,2, Andreas
Peukert3, Alina Chanaewa3, and Elizabeth von Hauff3,4

1
Department of Physics, University of Isfahan, P.O. Box 81746-7344, Isfahan, Iran
2
Quantum Optics Research Group, University of Isfahan, Isfahan, Iran
3
Institute of Physics, University of Freiburg, Freiburg, Germany
4
Physics of Energy, Department of Physics and Astronomy, Vrije University Amsterdam, Amsterdam, Netherlands

Received 30 November 2014, revised 5 January 2015, accepted 3 February 2015

Published online February 2015

Keywords Ag nanoparticles, plasmonics, organic solar cells, low band gap polymer, optical simulation
__________________________ 

* Corresponding author: e-mail moh1135@gmail.com, Phone: +983137934728, Fax: +983137932409 

1 Description of samples

2 Absorption spectra of the samples

3 Analysis of SEM data to determine distribution in particle size

4 Determining particle height from AFM data and modeling

5 Additional FDTD simulations

6 Dark J-V characteristics of different [2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-

dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)](PCPDTBT):C70BM solar cells

References

1 Description of samples

Samples were prepared by thermally evaporating Ag onto substrates. The description of the sample structures is
given in Table S1. The structure of investigated OSCs is shown in Fig. S1.
 

Table S1 Sample parameters.

Spin casting of
Sample Thickness of Annealing of silver at PEDOT:PSS
Type of substrate
no. film (nm) 200 °C for 15 min followed by
annealing

1 Glass-ITO 2 -- √
A* Glass-ITO 2 √ √
3 Glass-ITO 5 -- √
B* Glass-ITO 5 √ √
5 Glass 5 √ --
*
This type of anode structure was used for OSC fabrication.

Figure S1 Schematic illustration of investigated OSCs. The inset shows the computational domain used for FDTD
simulation of separated NP.

2 Absorption spectra of the samples

Figure S2 Absorption spectra of the samples investigated here. For comparison, the absorption spectrum of reference
glass/ITO sample with a layer of PEDOT: PSS is also shown.

Samples 1 and 3 do not exhibit pronounced features indicating that as-deposited layers are not separated particle-
like. After the Ag layer annealing, peaks emerge for samples A, B and 5, which is indicative of the localized
surface plasmon resonance of the metal NPs. Compared to the LSRP band of sample A, the plasmonic
 

absorption band of sample B is shifted to the higher wavelengths and is broader. The higher FWHM of the band
indicates a broader size distribution, which is consistent with the SEM analysis. The position of the plasmonic
band is also sensitive to the dielectric constant of the surrounding media. The typical refractive index of ITO and
PEDOT:PSS (1.8 and 1.56) are higher than the refractive index of glass and air (1.5 and 1) [1], leading to a red
shift in the peak from sample B compared to sample 5.

3 Analysis of SEM data to determine distribution in particle size

ImageJ was used to analyze the particle width and distribution. Figures S3 and S4 show the re-coloured SEM
image of sample A, and its area distribution, respectively.

Figure S3 Re-coloured SEM image of sample A for analysis with ImageJ.

Table S2 The frequency table of NP’s

area of sample A

Number 
No.  NP’s area 
of NP 
12.952* 
1  Mean  96 
radius : 
~10 nm 
2  1243  18 
3  2473  17 
4  3703  8 
5  4933  5 
Figure S4 Area distribution of sample A with ImageJ surface 6  6163  1 
.
coverage . %, mean radius: .9 nm, average 7  7393  0 
center to center spacing: 7. nm . 8  8623  0 
12314.304 
  Mean 
9  1 
radius : 
 
~60 nm 
*The number of particle which their
areas located in this range:
[12.952 12.952 +1230.15] is 96,
 

Figure S5 Re-coloured SEM image of sample B with ImageJ.

Table S3 The frequency table of

NP’s area of sample B

Number 
  No.  NP’s area 
of NP 
10.797 
 
1  Mean  157 
radius : 
 
~10nm 
2 1321  70 
 
3 2631  37 
  4 3941  22 
5 5252  17 
  6 6562  9 
7 7873  5 
  8 10493  3 
9 11084  4 
Figure S6 Area distribution of sample B with ImageJ (surface coverage
14424.703 
10%, mean radius: 27 nm, average center to center spacing: 152 nm).
10  Mean  1 
radius : 
~65nm 

4 Determining particle height from AFM data and modelling

NanoScope analysis was used to analyze the particle height. Figure S7(a, b) shows the AFM image and section
analysis of sample A, respectively. Figure S8(a, b) shows the AFM image and section analysis of sample B,
respectively. For comparison, Fig. S8(c) shows the AFM image of pure ITO.
 

a 

Figure S7 (a, b) AFM image and section profile image of sample A by NanoScope (blue markers: vertical
distance 37.65 nm; red markers horizontal distance 23.59 nm).

a 
b

Figure S8 (a, b and c), (a, b) AFM image and section profile of AFM image of sample B by
NanoScope (blue markers: vertical distance 38.61 nm; red markers horizontal distance 22.73 nm).
(c) AFM image of pure ITO.

Due to the roughness of the ITO, an exact determination of particle height is difficult with AFM. For this reason
we used a model to extract the particle heights.

Bedeaux et al. proposed a model for the far field behaviour of thin films with thicknesses in the subwavelength
regime [2]. From this the Fresnel coefficients as well as parameters of the nanostructures can be determined.
Lazzari et al. expanded on this model for films composed of simple shapes such as truncated spheres with an
axis of revolution normal to the surface of the substrate, and dipole-quadrupole interactions between particles
[3]. The system, which is considered by this model, is depicted in Fig. S9. According to the mean radius and
average center to center spacing which they are extracted from ImageJ toolbar, by matching the experimental
 

absorption peaks and results of this model, the height of particles were estimated (R┴ = 30 nm, tr=0.15 and R┴ =
30nm, tr= -0.24 for samples A and B, respectively). The simulated absorption spectrum by this model for
samples A and B are shown in Fig. S10.

Figure S9 The cross section of the Ag NPs on substrates as well as a single oblate spheroid island truncated (tr) by the
substrate.

Figure S10 The simulated absorption spectra of sample A and B.

5 Additional FDTD simulations

For more insight of near and far field effects, moreover the FDTD simulations in main text, the scattering and
absorption efficiencies as well as near field effect of truncated spheroid Ag were computed which NP was
located in the complete structure of organic solar cell (Fig. S11) based on mean radii and average center to center
distance (periodic boundary condition). Unless otherwise stated, all absorption and scattering cross-sections were
firstly computed and then they were normalized to geometrical cross section area (3.14 x R||2 ), for determining
related efficiencies.

The simulation zone consists of a three dimensional truncated spheroid Ag particle at interface between ITO and
PEDOT:PSS of the complete structure of solar cell. Perfectly matched layers (PML) boundary condition is used
along Y direction and periodic boundary conditions are used along X and Z directions. The light source is a
Gaussian-pulse source, which travels along the y-direction and is polarized along the x-direction. The Lorentz-
Drude values for Ag and Al were taken from this [4]. Complex refractive index of active layer of solar cell with
additive at related spectrum (PCPDTBT:PC70BM with with 2.5 vol% 1,8-octanedithiol as additive), was
extracted from this [5]. The particle height (H) was fixed at 34.5 nm (sample A) and 22.8 nm (sample B),
respectively. The particle radius (R||mean) and center to center distance were chosen from Fig. S4 (sample A) and
Fig. S6 (sample B), respectively.
 

Figure S11 Schematic illustration of 3D FDTD simulation zone of OSC.

The scattering and absorption efficiencies of the Ag NP for samples A and B are shown in Fig. S12(a) and
S12( b), respectively.
 

Figure S12 (a,b), (a) FDTD absorption and scattering efficiencies of truncated prolate spheroid Ag (sample A), (b) FDTD
absorption and scattering efficiencies of truncated oblate spheroid Ag (sample B).

Near field effects of Ag NP at solar cell with anode structure A, is shown in Fig. S13.
 

Figure S13 FDTD simulated electric field profile around truncated spheroid Ag NP at plasmon resonance, that Ag NP was
located at the interface of ITO and PEDOT:PSS of solar cell with anode structure A.

6 Dark J-V characteristics of different PCPDTBT:C70BM solar cells

Figure S14 displays the dark J-V characteristics of PCPDTBT:PC 70 BM devices with and without Ag .

Figure S14 Dark J-V characteristics of PCPDTBT:PC 70 BM devices with and without Ag.

References

[1] L. Zhou et al., J. Phys. D: Appl. Phys. 47, 115504 (2014).

[2] B. Dick et al., Optical Properties of Surfaces (Imperial College Press, 2001).
[3] R. Lazzari et al., Thin Solid Films 419, 124 (2002).
[4] A. D. Rakic et al., Appl. Opt. 37, 5271 (1998).
[5] S. Albrecht et al., Org. Electron. 13(4), 615-622 (2012).