Solar Energy 214 (2021) 565–574

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Enhancing the efficiency of polymer solar cells by embedding Au@Ag NPs

Durian shape in buffer layer
Muheeb Ahmad Alkhalayfeh *, Azlan Abdul Aziz *, Mohd Zamir Pakhuruddin
School of Physics, Universiti Sains Malaysia, 11800 USM, Pulau Pinang, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Organic semiconducting polymers are useful in several photonic applications due to their tunable optical and
Polymer solar cell electronic properties and ease of fabrication. However, due to the short exciton diffusion length and low carrier
Plasmonic effect mobility of polymer solar cell (PSC) materials, their power conversion efficiency (PCE) is comparably lower than
Au@Ag NPs
their inorganic counterparts. Therefore, this study introduces plasmonic effects into these organic polymer-based
PEDOT:PSS
solar cells by incorporating Au@Ag nanoparticles (NPs) to improve their performance. The plasmonic NPs
(Au@Ag durian-shaped NPs), which can be placed in the hole transport layer (HTL) of the PSC, scatter light into
the active layer thereby increasing the optical path length of the incident light, leading to higher absorption and
short circuit current density of the PSCs. The shape of nanoparticles is an important factor since it directly affects
surface plasmonic resonance (SPR) and the incident light’s scattering. The proposed Au@Ag NPs (with many
sharp spikes) confirmed the effect of small radii of the spike ends of the durian-shaped NPs on the performance
PSCs. The results reveal that the embedded Au@Ag NPs improve the electrical properties of both the active layer
and HTL in PSCs. In more detail, Au@Ag NPs create plasmon-electrical effects which shorten transport path
length of the low-mobility holes and lengthen that of high-mobility electrons for better-balanced carrier
collection. Meanwhile, the resistance of HTL is reduced by Au@Ag NPs. Therefore Jsc and PCE of up to 17 mA/
cm2 and 3.73%, respectively, implies a 44.4% improvement in short-circuit photocurrent density and 49%
enhancement of the power conversion efficiency compared to the reference cell.

1. Introduction
Over the years, solar cells have transformed into an intrinsic part of
energy production. Solar cells constitute a crucial renewable energy
source that converts solar energy (i.e., sunlight) to electrical energy.
Organic photovoltaics (OPVs) or organic solar cells (OSCs), which
consist of a thin film of organic semiconductor materials, have garnered
immense interest as a potential substitute of their inorganic counterparts
for the production of inexpensive, clean and renewable energy. This
technology paves the way to employ them, particularly organic
polymeric-based solar cells (PSCs), in an extensive array of applications,
due to their exceptional properties, including the economic feasibility of
large-scale power generation; low weight; mechanical flexibility; and
great functional-tunability (Dou et al., 2013; Dehsari et al., 2014; Wang
et al., 2016; Holliday et al., 2017; Yan et al., 2018). However, due to the
short exciton diffusion length and low carrier mobility of PSC materials,
their power conversion efficiency (PCE) is comparably lower than their
inorganic counterparts (Mayer et al., 2007; Abdulrazzaq et al., 2013;
Yeh and Yeh, 2013; Feng et al., 2018). These solar cells are further
constrained by limited absorption of the incident light. Therefore,
diverse techniques of energy exploitation and storage, including addi­
tives, have been developed to boost the thin active layer’s absorption.
The inclusion of metallic nanoparticles (MNPs) to initiate localized
surface plasmon resonance (LSPR) is considered an effectual approach to
enhancing cell performance by improving light absorption with no
thickness expansion of the active layer (Notarianni et al., 2014; N’konou
et al., 2018; Gangadharan et al., 2017; Chen et al., 2018; Wang et al.,
2018; Liu et al., 2016; Liu et al., 2014). Gold (Au) and silver (Ag) are
distinctive as their free electron densities are within a precise range that
allows the SPR peaks of nanoparticles to be discernible from the visible
spectrum (Xia and Halas, 2005). In addition, it applies a dominant
photon scattering efficiency that expands the length of the photon path
within the cell. Several studies that evaluated the power conversion
efficiency of polymer solar cells reported marked improvement by
incorporating Au and/or Ag nanoparticles into the photovoltaic layers
either into the active layers, buffer layers, or interfacial layer between

* Corresponding authors.
E-mail addresses: muheebphy@yahoo.com (M.A. Alkhalayfeh), lan@usm.my (A.A. Aziz).

https://doi.org/10.1016/j.solener.2020.12.010
Received 12 October 2020; Received in revised form 3 December 2020; Accepted 5 December 2020
Available online 29 December 2020
0038-092X/© 2020 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
M.A. Alkhalayfeh et al.
Fig. 1. The whole procedure of durian-shaped Au@Ag NPs synthesis using AA as reducing agent.
the buffer layer and active layer (Xu et al., 2020; Babaei et al., 2020;
Koul et al., 2020; Nair et al., 2020; Ali et al., 2020; Sun et al., 2020; He
et al., 2015). Nonetheless, the scattering efficiency of Au NPs is rela­
tively lesser compared to its level of self- absorption. On the contrary,
the scattering efficiency of Ag NPs is comparably high, although the
LSPR region is restricted to a wavelength range of 400–500 nm. Thus,
maintaining the broad wavelength range, especially at long wave­
lengths, is a complex process. Furthermore, the LSPR effect phenomenon
using mixtures of Au and Ag NPs has not been fully elucidated (Tran
et al., 2020; Xu et al., 2014; Gao et al., 2017; de Souza et al., 2018). The
Au and Ag NPs present an intense enhancement of the electric field at
low and high energies, respectively, which is a dilemma that is
encountered when using mixtures of Au and Ag NPs. In addition, the
absorption, scattering of the incident light, and LSPR effect of the NPs
are strongly dependent on their shapes, sizes, and distribution (Xia and
Halas, 2005; Tseng et al., 2015).
In this study, a new type of plasmonic cores was proposed to improve
the efficiency of polymer solar cells. Durian-shaped Au@Ag NPs (with
many sharp spikes) were prepared in order to examine the effect of the
small radii of the ends of spikes on performance polymer solar cell. This
is imperative as the plasmonic effect of sharp spikes in polymer solar
cells is yet to be investigated. Furthermore, the plasmonic effect of
Au@Ag NPs in the buffer layer was investigated in order to demonstrate
the combinatorial impact of the high scattering power of Ag NPs and the
broad spectral response of Au NPs at the long-wavelength range. This
will improve the LSPR effects and increase light absorption in the active
layer.
2. Experimental
2.1. Materials
Silver nitrate (AgNO3, 99%), Gold (III) chloride trihydrate
(HAuCl4.3H2O, 99.9%), ascorbic acid (AA, 99.7%), poly­
vinylpyrrolidone with M mass 10− 4 g/mol (PVP), and indium-tin-oxide
(ITO) coated glasses with a sheet resistance of 15–25 Ω/sq were pur­
chased from Sigma–Aldrich. Acetone, isopropyl alcohol (IPA), and
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ethanol were used for clean ITO glass. Zinc metal (Zn) and hydrochloric
acid (HCl) were used for etching ITO electrod from some parts of the
glass slide to avoid shorts. The active layer composition [4,8-bis[(2-
ethylhexyl) oxy] benzo [1,2-b:4,5-b’] dithiophene-2,6-diyl] [3-fluoro-
2-[(2-ethylhexyl) carbonyl]thieno[3,4-b] thiophenediyl (PTB7), and
[6,6]-Phenyl C71 butyric acid methyl ester, mixture of isomers (PC71 BM)
were solved in chlorobenzene (CB) and 1,8-diiodooctane. poly(3,4-ethyl
enedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) was pur­
chased from Sigma–Aldrich. Ultra-pure deionized (DI) water was used
for all the experimental solutions.
2.2. Synthesis of Au@Ag NPs durian-shaped
Durian-shaped Au@Ag nanoparticles were synthesized of an
aqueous solution of Au and Ag compounds. Firstly, 20 μl of a 10 mM
AgNO3, 200 ml of 10 mM HAuCl4 was added to 10 ml DI water. After­
wards, AA (100 mM) solutions with different molar concentration ratios
(30 μl (Au@Ag-30), 35 μl (Au@Ag-35), 40 μl (Au@Ag-40), and 45 μl
(Au@Ag-45)) were added. The resultant solution was stirred and
pipetted manually for 20 s. The successful formation of durian-shaped
Au@Ag NPs is confirmed by the blue colour of the final solution.
Lastly, 2 mg of PVP dissolved in 80 μl of water was added to the solution
as a stabilizing agent. The schematic of the durian-shaped Au@Ag NPs is
depicted Fig. 1.
2.3. Devices fabrication
The fabrication of organic solar photovoltaic that entails several vital
steps; is explained in detail below.
2.3.1. ITO etching and Cleaning
ITO is utilized as an anode because of its remarkable characteristics
which include low sheet in the range of 15–25 Ω/sq. and high optical
transmittance (more than 85%). To avert defects or interruptions, ITO
should be removed from parts of the glass slide (particularly the margins
of the substrate). The substrate was immersed in hydrochloric acid,
followed by the zinc powder’s addition to speed up the reaction. After
M.A. Alkhalayfeh et al.
Fig. 2. (a) The schematic structure of a solar cell with Au@Ag NPs doped buffer layer. (b) The real photo of fabricated solar cells. The position of the ITO layer was
marked by highlight line and the device area, which is defined by the overlapped area of the Al layer and ITO layer, was about 0.25 cm2.
the etching process, the substrates are washed in deionized water to
dispel the acid. The cleaning procedure for eliminating the artefacts
(stains, grease, dust, oil, and residues) of organic solvents from the
glassware and substrate includes: (1) cleaning with soap solution in an
ultrasonic bath for 10 min to eradicate stain and dust, followed by im­
mersion in de-ionized water to remove soap remains, (2) cleaning with
acetone in an ultrasonic bath for 20 min to remove oil and grease, (3)
cleaning with iso-propyl alcohol, ethanol, and DI water, successively, in
an ultrasonic bath for 20 min to eliminate organic residues, and then
aerated in a vacuum oven at 100◦ C for 15 min to remove organic sol­
vents used in cleaning procedure, (4) and lastly, the dried glass was
subjected to oxygen plasma treatment to overcome the high surface
energy of the ITO.
2.3.2. Spin coating of PEDOT: PSS mixed by Au@Ag NPs
PEDOT:PSS is utilized as a hole transport layer (HTL) because of its
high transparency in the visible range, lasting stability, simple pro­
cessing, and non-hazardous nature (Huang et al., 2005). Hence, it has
evolved into an excellent option for interfacial/electrode material in
several applications that include PSCs (Mohammad et al., 2019; Ismail
et al., 2016; Hu et al., 2018; Said et al., 2019). The PEDOT:PSS solution
was filtered through a 0.45 μm nylon filter to obtain a good film quality.
The film thickness was optimized at 40–100 nm, which can be attained
by using the spin-coating technique. In this study, the Au@Ag NPs
prepared were distributed uniformly in HTL and were deposited without
agglomeration on the ITO substrates which then rotated at 3500 rpm for
a duration of 30 s. To achieve the optimized performance of the PSC, the
volume ratio of PEDOT:PSS and Au@Ag NPs were set at 10%. The
centrifugal forces enabled the coating of the homogeneous PEDOT:PSS
film (thickness of 40 nm). Lastly, the cells were annealed using a hot
plate set at 70◦ C for 2 h to dispel the surplus water molecules from the
samples and enhance the adhesion between composites films and ITO on
a glass substrate.
2.3.3. Films preparation of PTB7:PC71 BM
Here, the weights of the solid components of PTB7 and PC71 BM were
obtained inside the glove box to achieve the ultimate solution concen­
tration of 10 mg/ml and 15 mg/ml, respectively. Chlorobenzene and
1,8-diiodooctane solvents are frequently utilized to enable a good sol­
ubility of PTB7:PC71 BM at a volume ratio of 97:3, respectively. The
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solution was stirred overnight in a glove box. PTB7 is preferred because
of their red-shifted UV absorption, narrower optical bandgap, and good
combination with all PSCs (He et al., 2015; Li and Brabec, 2015; Wan
et al., 2016). The last step involved the deposition of an active layer on
PEDOT:PSS through a 0.2 μm polytetrafluoroethylene (PTFE) filter
using the spin-coating technique (1000 rpm for 30 s) to obtain a thick­
ness of 100 nm.
2.3.4. Electrode preparation
The thickness of the electrode plays a significant part in the accretion
of electrons, since thickness increases with series resistance, thus leading
to recombination of the excitons, which adversely affects the cell’s
performance. This study selected Al with a thickness of 100 nm at
pressures less than 4.5 × 10− 5mbar due to its cost-effectiveness and
techno-friendliness. Five categories of solar cells (with only PEDOT:PSS,
with Au@Ag-30/PEDOT:PSS, with Au@Ag-35/PEDOT:PSS, with
Au@Ag-40/PEDOT:PSS and Au@Ag-45/PEDOT:PSS) were constructed
in the experiment. The schematic structure of a polymer solar cell device
is depicted in Fig. 2a, while a real picture of solar cells fabricated in this
study is shown in Fig. 2b.
2.4. Samples characterization and measurements
Transmission electron microscopy (TEM) and field emission scan­
ning electron microscopy (FESEM) were used to determine morpho­
logical variations and size of the durian-shaped Au@Ag NPs. Prior to the
TEM analysis, drops of Au@A NPs colloids were mounted onto a carbon-
coated copper grid and dried under ambient conditions. The absorption
spectra of the multilayer film of ITO/PEDOT:PSS/ PBT7:PC71BM with
and without Au@Ag NPs in the PEDOT:PSS layer were measured using
UV–vis spectrophotometer at room temperature. The PEDOT:PSS’s
surface morphology with and without Au@Ag NPs, was also analyzed
using atomic force microscopy (AFM) by means of a Bruker Dimension
Edge microscope that functions in the dynamic force mode at room
temperature and controlled by computer software (Nova Px). Directly
after fabrication, the current–voltage (I-V) properties of PEDOT:PSS
were measured under room temperature and atmospheric pressure
without any device encapsulation, by using a computer-controlled
Keithley 2400 source measurement unit and solar simulator under AM
1.5G illumination (1000 W⋅m− 2).
M.A. Alkhalayfeh et al. Solar Energy 214 (2021) 565–574

Fig. 3. FESEM images of (a) Au@Ag-30, (b) Au@Ag-35, (c) Au@Ag-40, and (d) Au@Ag-45.

Fig. 4. TEM images of (a) Au@Ag-30, (b) Au@Ag-35, (c) Au@Ag-40, (d) Au@Ag-45, and Au@Ag-50.

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Fig. 5. Size distributions of the synthesized Au@Ag NPs.

3. Results and discussion

2HAuCl4 + 3C6 H8 O6 →2Au0 + 3C6 H6 O6 + 8HCl
3.1. Morphology study
This reaction occurs immediately the L-ascorbic acid is added to HAuCl4
under ambient conditions. In addition, several studies have explored
As earlier mentioned, durian-shaped Au@Ag NPs were synthesized
size-controlled synthesis of Au NPs (Sun et al., 2009; Annur et al., 2018;
via the reduction of a solution comprising a mixture of HAuCl4, AgNO3
Annur et al., 2018). On the other hand, Ag ions on the surface of Au NPs
and ascorbic acid (AA). The formation of durian-shaped and NPs was
have a lower tendency of reduction than Ag+/Ag0, even though ascorbic
achieved through the modification of concentration ratio between
acid is unable to reduce Ag+ at low pH (Chen and Liu, 2011).In the mix
HAuCl4, AgNO3, and AA (keeping a constant concentration of HAuCl4
solution, Au ions are first reduced by ascorbic acid to generate Au NPs,
and AgNO3 and changing the amount of AA). Ascorbic acid (AA) serves
because of their higher potential for reduction than Ag ions. As a result,
as a reducing agent, e.g. L-ascorbic acid donates the electrons to reduce
the Ag ions would be reduced on the surface of Au NPs, thus acting as
Au+3 to Au0, as expressed in the equation below (Sun et al., 2009):
seeds or active sites for additional growth. Due to Ag ions’ catalytic

Fig. 6. FESEM image and EDX spectra of the Au@Ag-40 NPs.

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Fig. 7. The AFM topographical images (4 μm × 4 μm) of HTLs (a) PEDOT:PSS only, (b) Au@Ag-30, (c) Au@Ag-35, (d) Au@Ag-40, (e) Au@Ag-45.

effect, Au grows from these active sites on the surface of Au NPs (Cheng
et al., 2012). The FESEM images of the fully developed Au@Ag NPs with
four different sizes (Au@Ag-30, Au@Ag-35, Au@Ag-40, and Au@Ag-
45) are presented in Fig. 3. It can be inferred from the FESEM micro­
graphs that the durian-shaped (sharp spikes) Au@Ag NPs becomes more
distinct as the concentration ratio of ascorbic acid reaches 40 μl (Fig. 3c).
Fig. 4 presents the transmittance electron microscopy (TEM) images
of Au@Ag core/shell nanostructure. The observable small dark particles
denote the presence of Au NPs. The TEM images also indicate homog­
enous dispersion of the NPs devoid of agglomeration. The particle size
range of the NPs was determined through measurement of the particles’
diameters using the ImageJ processing program. The durian shapes’
dimensions were measured as the diameter of the circle, as shown in
Fig. 5. The average particle sizes of Au@Ag-30, Au@Ag-35, Au@Ag-40,
Au@Ag-45, and Au@Ag-50, are 39, 47, 51, 58 and 116 nm, respectively.
Similar to the FESEM images, sharp spikes of the Au@Ag NPs became
more discernible from the TEM images at AA concentration of 30 μl
(Fig. 4a), and were more evident at AA concentration of 40 μl (Fig. 4c).
Further observations indicate that an increase in the concentration ratio
of AA to 50 μl resulted in the emergence of considerable amount of semi-
Fig. 8. XRD of Au@Ag-40 NPs.
spherical NPs (disappearance of the sharp spikes) and increased size of
the NPs (Fig. 4d). The increase in size of Au@Ag NPs with increasing AA
formation of Au@Ag NPs film over PEDOT:PSS. The mean square (rms)
concentration can be attributed to the gradual enveloping of the NPs by
roughness values for PEDOT:PSS coated on ITO, without and with the
the electrolyte (AA).
addition of Au@Ag NPs, were 1.1 nm and 10.3 nm, respectively. The
Spot energy dispersive X-ray (EDX) analysis was performed on the
variation in rms may be due to the particle sizes of the added Au@Ag
(1) core and (2) shell of the NPs, as shown in Fig. 6. Based on the peak
and sharp spikes that are embedded in PEDOT:PSS film after the inclu­
intensity (cps/eV), EDX analysis shows a sufficient increase in Ag con­
sion of Au@Ag NPs. In addition, the increase in roughness with the in­
tent in the Au@Ag NPs between the two points, indicating the successful
clusion of Au@Ag NPs can reduce the diffusion length of electrons so
reduction of the added Ag precursors sharp spikes on the Au surface.
that they can be propagated to the active layer, thus facilitating charge
Similar to the SEM and TEM results (Figs. 3 and 4), the EDX confirms the
transfer (Chen et al., 2018; Babaei et al., 2020; Rezaei et al., 2019;
successful synthesis of Au@Ag core/shell nanostructure.
Otieno et al., 2017). Furthermore, the sharp spikes of Au@Ag NPs can
Fig. 7 shows 2D AFM images were obtained before and after the

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M.A. Alkhalayfeh et al.
Fig. 9. UV–vis absorption spectra of the PSCs with and without incorpo­
rated NPs.
penetrate the active layer which increases both the number of excitonic
generation and field near the interface between PTB7 and PC71 BM, thus
increasing the exciton dissociation.
The crystal structure of the synthesized Au@Ag NPs was further
explored using X-ray diffraction (XRD), as shown in Fig. 8. The XRD
spectra of the Au@Ag core/shell nanostructure exhibit similar diffrac­
tion peaks. For Au NPs, the peaks at 2θ = 38.1◦ , 44.3◦ and 64.5◦ denote
(111), (200) and (220) crystal faces (ICSD card No. 01–089-3697),
respectively. On the other hand, the Ag NPs show diffraction peaks at 2θ
= 37.9◦ , 44.1◦ and 64.6◦ that signify (111), (200) and (220) crystal faces
(ICSD card No. 00–001-1164). This indicates that both Au and Ag have
face-centered cubic structures.
Fig. 10. Schematic structure of working of polymer solar cells.
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Solar Energy 214 (2021) 565–574
3.2. UV–vis spectroscopy
In order to directly explore LSPR effects and clarify the light ab­
sorption improvement with inclusion of the plasmonic component,
UV–vis absorption spectra of the layers, with and without Au@Ag NPs,
were compared as shown in Fig. 9. The LSPR effect of metal NPs is
dependent on the wavelength properties (Wu et al., 2011). The strong
LSPR field proximate to the surface and vicinity of the metallic NPs is
enhanced within a broad wavelength range. Evidently, compared to the
reference cell, the light absorption properties in the device’s photoactive
layer embedded plasmonic NPs have been enhanced in the broadband
region of 300 to 800 nm. The increase in broad absorption may be
attributed to the large field intensity in PTB7:PC71 BM resulting from the
small radii of the tips of the spikes that penetrate the active layer (Ren
et al., 2016; Ginting et al., 2017), and elongated optical path length in
the active layer caused by the plasmonic enhanced scattering effects of
the portion metallic NPs in PEDOT:PSS layer (Tran et al., 2020; Chang
et al., 2018). The maximum enhancement of the absorption is observed
when the ratio Au:Ag was 40μl (Au@Ag-40 (green curve)) due to the
higher number of sharp spikes (compared to the other ratios), as shown
in Fig. 9. As aforementioned, the enhanced absorption is attributed to
the increased absorption in the active layer, thus enhancing the pro­
duction of excitons in PSCs.
3.3. Principle of polymer solar cells
The conversion of light-absorption into free-charge carriers is the key
disparity between conventional inorganic devices and polymer-based
solar cells. For example, the absorption of light in conventional inor­
ganic materials results in the generation of free electrons and holes.
Contrarily, upon light absorption, polymer-based materials produce
bound electron-hole pairs that are referred to as excitons. Thus, the
generation, transport, and accretion of charges differ between polymer
solar cells and inorganic devices. The fundamental principle of photo­
current generation inside PSCs is based on these key steps: light ab­
sorption and excitons generation; diffusion of excitons to active
interfaces, charge separation, and charge transport and collection
(Chochos and Choulis, 2011; Facchetti, 2013; Mazzio and Luscombe,
2014; Marinova et al., 2017). The direct conversion of light incident on
M.A. Alkhalayfeh et al.
Fig. 11. Current density versus voltage analysis of PSCs with Structures ITO/
PEDOT:PSS with and without Au@Ag-(30,35,40,and 45) NPs/PTB7:PC71 BM,
AM 1.5G illumination at 100 mW/cm2.
polymer solar cells into electricity requires an active layer composed of
two photoactive materials to enable optical absorption and production
of excitons. The active and buffer layers are inserted between the anode
and cathode that accumulate the free charge carriers as illustrated in
Fig. 10. The transparency of ITO and PEDOT:PSS allows the transmission
of the incident light into the active layer (PTB7:PC71 BM). The absorp­
tion of incident light at PTB7 (donor) initiates the generation of excitons
which can diffuse into the PC71 BM (acceptor) layer or dissociated at the
interface layer between PTB7 and PC71 BM. The dissociation arises when
the time of diffusing excitons exceeds the duration of decomposing the
excitons. Generally, the lifetime of an exciton is determined to be about
several nanoseconds. The exciton diffusion length in organic materials
varies between 1 and 10 nm, which critically constrains the thickness of
absorbing layer (Rafique et al., 2018). Conversely, polymer materials
typically have narrow absorption spectra with no optical absorption in
the spectrum’s red and near-infrared sections. Therefore, to enhance the
efficiency of OPV cells, there is the need to increase both the number of
excitons generated in PTB7 and the field near the interface layer be­
tween PTB7 and PC71 BM with the aim of increasing the dissociation of
excitons. LSPR of Au@Ag NPs embedded in PEDOT:PSS increases the
electric field in the region of the sharp spikes of Au@Ag NPs, which in
turn improves the integral electric field at the interface between PTB7
and PC71 BM which contributes to the decomposition of excitons. This
Fig. 12. (a) Short circuit current density (Jsc), b) Power conversion efficiency (PCE) of Au@Ag-30,Au@Ag-35, Au@Ag-40, Au@Ag-45 NPs, samples.
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technique is valuable for OPV because of their short diffusion length.
Thus, the insertion of Au@Ag NPs in PEDOT:PSS contributes to
increasing the densities of excitons that match the resonance. Addi­
tionally, the use of NPs with numerous sharp spike and edges as plas­
monic cores enables the attainment of a greater field improvement.
3.4. Performance of PSCs incorporating Au@Ag like durian shape NPs
The current density–voltage (J–V) properties of the polymer solar
cells were investigated upon subjecting them to solar simulator (AM1.5
G). The photovoltaic response of the devices with the structure of glass/
ITO/PEDOT:PSS (with or without Au@Ag NPs)/PTB7:PC71 BM/Al are
illustrated in Fig. 11. In the absence of Au@Ag NPs, the polymer solar
cells exhibit a short-circuit current density (Jsc), and the open-circuit
voltage (Voc) of 11.82 mA/cm2 and 0.68 V, respectively. As observed
in Fig. 11, after the inclusion of Au@Ag NPs, the devices’ short-circuit
current density parameters were improved. For Au@Ag-40 NPs in
PEDOT:PSS, optimum Jsc = 17.07 mA/cm2 was obtained, which is
considerably higher than that of the device without Au@Ag NPs. This
can be attributed to an increase in the effect of the LSPR due to the size of
Au@Ag NPs and number of sharp spikes, thus improving absorption of
the active layer, which is consistent with the UV–vis absorption results
(Fig. 9). Meanwhile, the Voc parameter was also employed to evaluate
the performance of the solar cells. The Voc parameters indicated that the
performance of the PEDOT:PSS device was slightly enhanced with the
embedding of Au@Ag NPs as compared to the reference cell (without
Au@Ag NPs). Nonetheless, a gradual increase in Jsc is observed with the
incorporating of Au@Ag NPs in PEDOT:PSS (Au@Ag-30 NPs, Au@Ag-
35 NPs, and Au@Ag-40 NPs), however, the Jsc begins to decrease as
the size increases to 58 nm (Au@Ag-45 NPs), which may be attributed to
the concomitant increase in particle size which led to high reflectance of
the incident solar light.
The electric power derived from a photovoltaic cell is dependent on
the Jsc and Voc of the device, and the fill factor (FF) at a given incident
power (Pin) based on the formula of power conversion efficiency (PCE)
expressed below:
PCE = Jsc ⋅Voc ⋅FF/Pin
Where the fill factor (FF) is defined as the ratio of the maximum
power from the heterojunction solar cell to the product of Voc and Jsc (FF
= Jmax ⋅ Vmax/Jsc ⋅ Voc). The maximum current (Jmax) and voltage (Vmax)
were obtained at the maximum output power point. Fig. 12a and b show
the current density–Au@Ag NPs content curve and the PCE–Au@Ag NPs
content curve, respectively. It can be inferred from Fig. 12a and b that
the incorporation of Au@Ag NPs affects the Jsc and PCE of solar devices.
M.A. Alkhalayfeh et al. Solar Energy 214 (2021) 565–574

Table 1 4. Conclusion
Photovoltaic parameters of PSCs embedded with and without Au@Ag NPs.
samples JSC VOC Jmax Vmax FF PCE This study investigated the effect of incorporating the spiky, durian-
(mA/ (V) (mA/ (V) (%) (%) shaped plasmonic Au@Ag NPs into PEDOT:PSS on photovoltaic cells’
cm2) cm2) performance. The small radii of the spike ends of Au@Ag NPs signifi­
(1) ITO/PEDOT: 11.82 0.68 6.27 0.4 30.9 2.5 cantly enhance the electromagnetic field at their locations, which
PSS/PTB7: considerably improves PSCs’ efficiency. The experimental results reveal
PC71BM that the devices with a structure ITO/PEDOT:PSS (Au@Ag-40 NPs)/
(2) ITO/PEDOT: 15.28 0.69 8.07 0.4 30.3 3.22
PSSS(Au@Ag-
PTB7:PC71 BM/Al demonstrated optimal Jsc and PCE. This research
30)/PTB7: confirms that Au@Ag NPs embedded into HTL offers a higher interfacial
PC71BM area and more enhanced UV–vis light absorption of devices in the active
(3) ITO/PEDOT: 15.77 0.69 8.37 0.4 30.5 3.35 layer. The results also reveal that the embedded Au@Ag NPs can
PSSS(Au@Ag-
improve the electrical properties of both the active layer and HTL in
35)/PTB7:
PC71BM PSCs, with Jsc and PCE of up to 17 mA/cm2 and 3.73%, respectively. This
(4) ITO/PEDOT: 17.07 0.69 9.32 0.4 31.3 3.73 study recommends investigating the effect of Au@Ag NPs with many
PSSS(Au@Ag- sharp spikes in the active layer, after deposition of the SiO2 layer on
40)/PTB7: these particles to avoid harmful direct contact between active layer and
PC71BM
(5) ITO/PEDOT: 14.82 0.69 7.81 0.4 30.2 3.12
metallic NPs.
PSSS(Au@Ag-
45)/PTB7: Declaration of Competing Interest
PC71BM
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
Table 2 the work reported in this paper.
Comparison table showing efficiency enhancement of different structures of
plasmonic NPs in PSCs studied by other researchers. Acknowledgement
number Device geometry Improvement in Ref.
PCE (%) This work was supported by the Ministry of Higher Education
1 ITO/ PEDOT:PSS + Au nanosphere 24 Said et al. Malaysia (MOHE), FRGS Grant [203/PFIZIK/6711768], and the authors
(NS)/CuPc/C60/Al (2019) would also like to thank School of Physics, Universiti Sains Malaysia, for
2 ITO/Au@PDA/ZnO/PTB7:PC71 30 Xu et al. access to supporting facilities related this research work.
BM/MoO3/Al (2020)
3 ITO/ZnO + AgNS/PTB7:PCBM + 15 Nair et al.
References
AgNS/MoO3/Ag (2020)
4 ITO/PEDOT:PSS + Ag NS/ 33 Chang et al.
Abdulrazzaq, O.A., Saini, V., Bourdo, S., Dervishi, E., Biris, A.S., 2013. Organic solar
P3HT:PC61 BM/Al (2018)
cells: a review of materials, limitations, and possibilities for improvement. Part. Sci.
5 ITO/PEDOT:PSS + Ag- 12 Chen et al. Technol. 31 (5), 427–442.
decahedron/PTB7/PC71 BM/Ca/Al (2018) Ali, A., Said, D., Khayyat, M., Boustimi, M., Seoudi, R., 2020. Improving the efficiency of
6 ITO/PEDOT:PSS + Ag NSs/CuPc/ 39 Ali et al. the organic solar cell (CuPc/C60) via PEDOT: PSS as a photoconductor layer doped
C60/Al (2020) by silver nanoparticles. Results Phys. 16, 102819.
7 ITO/Au: Ag/MoO3/DBP/C70/ 22.5 Gao et al. Annur, S., Santosa, S.J., Aprilita, N.H., 2018. pH dependence of size control in gold
Bphen/Al (2017) nanoparticles synthesized at room temperature. Orient. J. Chem. 34 (5), 2305–2312.
Annur, S., Santosa, S., Aprilita, N.H., Phuong, N.T., Phuoc, N., 2018. Rapid synthesis of
8 ITO/PEDOT:PSS + Au nanostars/ 10.7 Ren et al.
gold nanoparticles without heating process. Asian J. Chem. 30 (11), 2399–2403.
PTB7:PC71 PM/Al (2016)
Babaei, Z., Rezaei, B., Pisheh, M.K., Afshar-Taromi, F., 2020. In situ synthesis of gold/
9 ITO/PEDOT:PSS + Au@Ag 18 Baek et al. silver nanoparticles and polyaniline as buffer layer in polymer solar cells. Mater.
nanocubes (NC)/PCDTBT:PC71 (2014) Chem. Phys. 122879.
BM/Al Baek, S.-W., Park, G., Noh, J., Cho, C., Lee, C.-H., Seo, M.-K., Song, H., Lee, J.-Y., 2014.
10 This experiment 49 – [au@ ag] core–shell nanocubes for efficient plasmonic light scattering effect in low
bandgap organic solar cells. ACS Nano 8 (4), 3302–3312.
Chang, F., Li, H., Zheng, B., Qian, K., Lei, Q., Han, G., Song, Y., Shao, P., 2018. Effect of
silver nanospheres embedded in buffer layer based on organic solar cells. J. Mater.
Table 1 summarizes the different performance parameters Jsc, Voc, Sci.: Mater. Electron. 29 (2), 1349–1355.
FF, Jmax, Vmax and PCE of the devices, with and without Au@Ag NPs. Jsc Chen, H.M., Liu, R.-S., 2011. Architecture of metallic nanostructures: synthesis strategy
and PCE were obviously enhanced after incorporating the Au@Ag NPs and specific applications. J. Phys. Chem. C 115 (9), 3513–3527.
Chen, C.-P., Lee, I.-C., Tsai, Y.-Y., Huang, C.-L., Chen, Y.-C., Huang, G.-W., 2018. Efficient
into PEDOT:PSS film. Jsc increased from 11.82 mA/cm2 to 15.28, 15.77, organic solar cells based on PTB7/PC_71BM blend film with embedded different
17.07, and 14.82 mA/cm2, and PCE increased from 2.5% to 3.22%, shapes silver nanoparticles into pedot: Pss as hole transporting layers. Org. Electron.
3.35%, 3.73%, and 3.12% when PEDOT:PSS was embedded with 62, 95–101.
Cheng, L.-C., Huang, J.-H., Chen, H.M., Lai, T.-C., Yang, K.-Y., Liu, R.-S., Hsiao, M.,
Au@Ag-30, Au@Ag-35, Au@Ag-40, and Au@Ag-45 NPs, respectively, Chen, C.-H., Her, L.-J., Tsai, D.P., 2012. Seedless, silver-induced synthesis of star-
which could be attributed to the modification of the PEDOT:PSS work shaped gold/silver bimetallic nanoparticles as high efficiency photothermal therapy
function by the addition of NPs (Otieno et al., 2017). This implies that reagent. J. Mater. Chem. 22 (5), 2244–2253.
Chochos, C.L., Choulis, S.A., 2011. How the structural deviations on the backbone of
the efficiency increases by 28%, 34%, 49%, and 25% when the PEDOT: conjugated polymers influence their optoelectronic properties and photovoltaic
PSS embedded by Au@Ag-30, Au@Ag-35, Au@Ag-40, Au@Ag-45 NPs performance. Prog. Polym. Sci. 36 (10), 1326–1414.
respectively. The results clearly indicate that Jsc and PCE of photovoltaic Dehsari, H.S., Shalamzari, E.K., Gavgani, J.N., Taromi, F.A., Ghanbary, S., 2014. Efficient
preparation of ultralarge graphene oxide using a PEDOT:PSS/GO composite layer as
cells are enhanced by incorporating Au@Ag NPs into PEDOT:PSS film,
hole transport layer in polymer-based optoelectronic devices. RSC Adv. 4 (98),
especially Au@Ag-40 NPs. Efficiency enhancement studied by re­ 55067–55076.
searchers using different plasmonic NPs applied in PSCs were also de Souza, M.L., dos Santos, D.P., Corio, P., 2018. Localized surface plasmon resonance
enhanced photocatalysis: an experimental and theoretical mechanistic investigation.
collected in Table 2 for comparison.
RSC Adv. 8 (50), 28753–28762.
Dou, L., You, J., Hong, Z., Xu, Z., Li, G., Street, R.A., Yang, Y., 2013. 25th anniversary
article: a decade of organic/polymeric photovoltaic research. Adv. Mater. 25 (46),
6642–6671.

573
M.A. Alkhalayfeh et al.
Facchetti, A., 2013. Polymer donor–polymer acceptor (all-polymer) solar cells. Mater.
Today 16 (4), 123–132.
Feng, L., Niu, M., Wen, Z., Hao, X., 2018. Recent advances of plasmonic organic solar
cells: Photophysical investigations. Polymers 10 (2), 123.
Gangadharan, D.T., Xu, Z., Liu, Y., Izquierdo, R., Ma, D., 2017. Recent advancements in
plasmon-enhanced promising third-generation solar cells. Nanophotonics 6 (1),
153–175.
Gao, Y., Jin, F., Su, Z., Zhao, H., Luo, Y., Chu, B., Li, W., 2017. Cooperative plasmon
enhanced organic solar cells with thermal coevaporated Au and Ag nanoparticles.
Org. Electron. 48, 336–341.
Ginting, R.T., Kaur, S., Lim, D.-K., Kim, J.-M., Lee, J.H., Lee, S.H., Kang, J.-W., 2017.
Plasmonic effect of gold nanostars in highly efficient organic and perovskite solar
cells. ACS Appl. Mater. Interfaces 9 (41), 36111–36118.
He, Y., Liu, C., Li, J., Zhang, X., Li, Z., Shen, L., Guo, W., Ruan, S., 2015. Improved power
conversion efficiency of inverted organic solar cells by incorporating Au nanorods
into active layer. ACS Appl. Mater. Interfaces 7 (29), 15848–15854.
He, Z., Xiao, B., Liu, F., Wu, H., Yang, Y., Xiao, S., Wang, C., Russell, T.P., Cao, Y., 2015.
Single-junction polymer solar cells with high efficiency and photovoltage. Nat.
Photon. 9 (3), 174–179.
Holliday, S., Li, Y., Luscombe, C.K., 2017. Recent advances in high performance donor-
acceptor polymers for organic photovoltaics. Prog. Polym. Sci. 70, 34–51.
Huang, J., Miller, P.F., Wilson, J.S., de Mello, A.J., de Mello, J.C., Bradley, D.D., 2005.
Investigation of the effects of doping and post-deposition treatments on the
conductivity, morphology, and work function of poly (3, 4-ethylenedioxythio­
phene)/poly (styrene sulfonate) films. Adv. Funct. Mater. 15 (2), 290–296.
Hu, W.-D., Dall’Agnese, C., Wang, X.-F., Chen, G., Li, M.-Z., Song, J.-X., Wei, Y.-J.,
Miyasaka, T., 2018. Copper iodide-PEDOT:PSS double hole transport layers for
improved efficiency and stability in perovskite solar cells. J. Photochem. Photobiol.,
A 357, 36–40.
Ismail, Y.A., Kishi, N., Soga, T., 2016. Improvement of organic solar cells using
aluminium microstructures prepared in PEDOT:PSS buffer layer by using ultrasonic
ablation technique. Thin Solid Films 616, 73–79.
Koul, S., et al., 2020. Investigation of non-ideality factors for a P3HT: PCBM based bulk
heterojunction organic solar cell in presence of silver nanoparticles. Trans. Electr.
Electronic Mater. 1–12.
Li, N., Brabec, C.J., 2015. Air-processed polymer tandem solar cells with power
conversion efficiency exceeding 10%. Energy Environ. Sci. 8 (10), 2902–2909.
Liu, C., Chang, K., Guo, W., Li, H., Shen, L., Chen, W., Yan, D., 2014. Improving charge
transport property and energy transfer with carbon quantum dots in inverted
polymer solar cells. Appl. Phys. Lett. 105 (7), 131_1.
Liu, C., Zhao, C., Zhang, X., Guo, W., Liu, K., Ruan, S., 2016. Unique gold nanorods
embedded active layer enabling strong plasmonic effect to improve the performance
of polymer photovoltaic devices. J. Phys. Chem. C 120 (11), 6198–6205.
Marinova, N., Valero, S., Delgado, J.L., 2017. Organic and perovskite solar cells: Working
principles, materials and interfaces. J. Colloid Interface Sci. 488, 373–389.
Mayer, A.C., Scully, S.R., Hardin, B.E., Rowell, M.W., McGehee, M.D., 2007. Polymer-
based solar cells. Mater. Today 10 (11), 28–33.
Mazzio, K.A., Luscombe, C.K., 2014. The future of organic photovoltaics. Chem. Soc. Rev.
44 (1), 78–90.
Mohammad, T., Bharti, V., Kumar, V., Mudgal, S., Dutta, V., 2019. Spray coated
europium doped PEDOT:PSS anode buffer layer for organic solar cell: the role of
electric field during deposition. Org. Electron. 66, 242–248.
Nair, A.T., Anoop, C., Vinod, G.A., Reddy, V., 2020. Efficiency enhancement in polymer
solar cells using combined plasmonic effects of multi-positional silver
nanostructures. Org. Electron. 105872.
574
Solar Energy 214 (2021) 565–574
N’konou, K., Peres, L., Torchio, P., 2018. Optical absorption modeling of plasmonic
organic solar cells embedding silica-coated silver nanospheres. Plasmonics 13 (1),
297–303.
Notarianni, M., Vernon, K., Chou, A., Aljada, M., Liu, J., Motta, N., 2014. Plasmonic
effect of gold nanoparticles in organic solar cells. Sol. Energy 106, 23–37.
Otieno, F., Shumbula, N.P., Airo, M., Mbuso, M., Moloto, N., Erasmus, R.M., Quandt, A.,
Wamwangi, D., 2017. Improved efficiency of organic solar cells using Au NPs
incorporated into PEDOT: PSS buffer layer. AIP Adv. 7 (8), 085302.
Rafique, S., Abdullah, S.M., Sulaiman, K., Iwamoto, M., 2018. Fundamentals of bulk
heterojunction organic solar cells: An overview of stability/degradation issues and
strategies for improvement. Renew. Sustain. Energy Rev. 84, 43–53.
Ren, X., Cheng, J., Zhang, S., Li, X., Rao, T., Huo, L., Hou, J., Choy, W.C., 2016. High
efficiency organic solar cells achieved by the simultaneous plasmon-optical and
plasmon-electrical effects from plasmonic asymmetric modes of gold nanostars.
Small 12 (37), 5200–5207.
Rezaei, B., Afshar-Taromi, F., Ahmadi, Z., Rigi, S.A., Yousefi, N., 2019. Enhancement of
power conversion efficiency of bulk heterojunction polymer solar cells using core/
shell, Au/graphene plasmonic nanostructure. Mater. Chem. Phys. 228, 325–335.
Said, D., Ali, A., Khayyat, M., Boustimi, M., Loulou, M., Seoudi, R., 2019. A study of the
influence of plasmonic resonance of gold nanoparticle doped PEDOT:PSS on the
performance of organic solar cells based on CuPc/C60. Heliyon 5 (11), e02675.
Sun, K., Qiu, J., Liu, J., Miao, Y., 2009. Preparation and characterization of gold
nanoparticles using ascorbic acid as reducing agent in reverse micelles. J. Mater. Sci.
44 (3), 754–758.
Sun, Y., Ren, G., Han, S., Zhang, X., Liu, C., Li, Z., Fu, D., Guo, W., 2020. Improving light
harvesting and charge extraction of polymer solar cells upon buffer layer doping.
Sol. Energy 202, 80–85.
Tran, Q.N., Lee, H.K., Kim, J.H., Park, S.J., 2020. Influence of gold–silver rough-surface
nanoparticles on plasmonic light scattering in organic solar cells. J. Nanosci.
Nanotechnol. 20 (1), 304–311.
Tseng, W.-H., Chiu, C.-Y., Chou, S.-W., Chen, H.-C., Tsai, M.-L., Kuo, Y.-C., Lien, D.-H.,
Tsao, Y.-C., Huang, K.-Y., Yeh, C.-T., et al., 2015. Shape-dependent light harvesting
of 3D gold nanocrystals on bulk heterojunction solar cells: plasmonic or optical
scattering effect. J. Phys. Chem. C 119 (14), 7554–7564.
Wan, Q., Guo, X., Wang, Z., Li, W., Guo, B., Ma, W., Zhang, M., Li, Y., 2016. 10.8%
efficiency polymer solar cells based on PTB7-Th and PC71BM via binary solvent
additives treatment. Adv. Funct. Mater. 26 (36), 6635–6640.
Wang, K., Liu, C., Meng, T., Yi, C., Gong, X., 2016. Inverted organic photovoltaic cells.
Chem. Soc. Rev. 45 (10), 2937–2975.
Wang, J., Jia, S., Cao, Y., Wang, W., Yu, P., 2018. Design principles for nanoparticle
plasmon-enhanced organic solar cells. Nanoscale Res. Lett. 13 (1), 1–6.
Wu, J.-L., Chen, F.-C., Hsiao, Y.-S., Chien, F.-C., Chen, P., Kuo, C.-H., Huang, M.H.,
Hsu, C.-S., 2011. Surface plasmonic effects of metallic nanoparticles on the
performance of polymer bulk heterojunction solar cells. ACS Nano 5 (2), 959–967.
Xia, Y., Halas, N.J., 2005. Shape-controlled synthesis and surface plasmonic properties of
metallic nanostructures. MRS Bull. 30 (5), 338–348.
Xu, M., Feng, J., Liu, Y.-S., Jin, Y., Wang, H.-Y., Sun, H.-B., 2014. Effective and tunable
light trapping in bulk heterojunction organic solar cells by employing Au-Ag alloy
nanoparticles. Appl. Phys. Lett. 105 (15), 160_1.
Xu, M., Yan, L., Zhu, Y., Li, Y., Song, X., Yin, L., 2020. Polydopamine-coated gold
nanoparticles used as modifier of the electron transport layer for PTB7:PC_71 BM
polymer solar cells. J. Mater. Sci.: Mater. Electron. 1–8.
Yan, C., Barlow, S., Wang, Z., Yan, H., Jen, A.K.-Y., Marder, S.R., Zhan, X., 2018. Non-
fullerene acceptors for organic solar cells. Nat. Rev. Mater. 3 (3), 1–19.
Yeh, N., Yeh, P., 2013. Organic solar cells: Their developments and potentials. Renew.
Sustain. Energy Rev. 21, 421–431.