4-fold photocurrent enhancement in ultrathin

nanoplasmonic perovskite solar cells

Boyuan Cai,1 Yong Peng,2,3 Yi-Bing Cheng,2,3 and Min Gu1,*
1
Centre for Micro-Photonics, Faculty of Engineering and Industrial Sciences, Swinburne University of Technology,
PO Box 218, Hawthorn, 3122 Victoria, Australia
2
State Key laboratory of Advanced Technologies for Materials Synthesis and Processing, Wuhan University of
Technology, Wuhan, Hubei, 430070, China
3
Department of Materials Science and Engineering, Monash University, Clayton, 3800 Victoria, Australia
*
mgu@swin.edu.au

Abstract: Although perovskite materials have been widely investigated for

thin-film photovoltaic devices due to the potential for high efficiency, their
high toxicity has pressed the development of a solar cell structure of an
ultra-thin absorber layer. But insufficient light absorption could be a result
of ultra-thin perovskite films. In this paper, we propose a new
nanoplasmonic solar cell that integrates metal nanoparticles at its rear/front
surfaces of the perovskite layer. Plasmon-enhanced light scattering and
near-field enhancement effects from lumpy sliver nanoparticles result in the
photocurrent enhancement for a 50 nm thick absorber, which is higher than
that for a 300 nm thick flat perovskite solar cell. We also predict the 4-fold
photocurrent enhancement in an ultrathin perovskite solar cell with the
absorber thickness of 10 nm. Our results pave a new way for ultrathin high-
efficiency solar cells with either a lead-based or a lead-free perovskite
absorption layer.
©2015 Optical Society of America
OCIS codes: (250.5403) Plasmonics; (310.6845) Thin film devices and applications;
(050.6624) Subwavelength structures; (350.6050) Solar energy.

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#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1700

Corrected: 10 December 2015

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1. Introduction
Perovskite based thin film solar cell has attracted increasing attention as a novel emerged
promising technology to harvest and convert sunlight to electricity efficiently [1, 2]. The
efficiency of the perovskite solar cell has been improved from 3.8% to as high as 20.1% since
the first published in 2009 [3–6]. However, there exists a severe challenge for the widespread
application of perovskite solar cells. A major concern is the toxicity of lead in the perovskite
materials. One way to solve this issue is to replace lead in the perovskite crystal with a less
toxic metal such as Sn [7, 8]. However, the Sn based perovskite material only delivers the
solar cell with an efficiency of around 6% due to the fast electron-hole recombination rate at
the defect sites in the absorber [8]. An alternative approach is to maintain the high
performance of the lead based perovskite solar cell with a much thinner absorber thereby
reducing the amount of lead in the material to minimize the detrimental effect on
environment. However previous studies have found that an optimum thickness for the
perovskite layer is about 300 nm, and films thinner than this would result in lower efficiency
due to insufficient light absorption [9, 10]. In this case, some novel light trapping strategies
should be applied for designing perovskite solar cells with extremely thin absorber layers.
Recently, plasmonic nanoparticles and nanostructures have been proven to be a useful
technology to enable solar cells to improve the efficiency with thin absorber film [11–16],
with most investigation ascribing the improvement to the enhanced light absorbance via the
plasmonic effects. The first mechanism is that plasmonic light scattering effect from the large
size particle is capable of redirecting the incident light into solar cells with increased light
path length [17, 18]. The second one is that when embedded with small metal particles, the
light absorption of the absorber can be enhanced due to the near field light concentration of
the nanoparticles through the localized surface plasmons [19, 20]. In this paper, to address the
challenging trade-off between the high absorbance and thinner absorber required for the
perovskite solar cells, plasmonic metal nanoparticles incorporated into the perovskite absorber
are investigated. First, near field light concentration effects of small Au and Ag particles are
explored with different particle radii, surface coverage (SC) densities and integrated positions

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1701
as shown in Figs. 1(a) and 1(b). Based on the optimization results of small metal particles, a
lumpy Ag nanoparticle model is proposed which consists of a large Ag particle as the core
particle with many small Ag particles decorated evenly outside the core particle together,
thereby providing both the plasmonic scattering and the plasmonic near field concentration
mechanisms. To fully utilize the plasmonic effects of the lumpy nanoparticles, the
nanoparticles are inserted in the perovskite absorber directly at the rear surface forming a
nanoshell structure for the absorber layer as shown in Fig. 1(d).

Fig. 1. Device schematics of the plasmonic perovskite solar cells. (a) With small metal
particles embedded in the perovskite absorber at the front surface. (b) With small metal
particles at the rear surface. (c) With lumpy nanoparticles at the rear surface. (d) The cross-
section of the solar cells embedded with the lumpy nanoparticle.

2. Results
The optical performance of the designed plasmonic perovskite solar cell structure is
conducted based on the finite difference time domain method (Lumerical FDTD solution). To
fully optimize the lumpy nanoparticles for solar cells, the sizes of both core and surface
nanoparticles need to be modified. Therefore, we first optimize the plasmonic light
concentration effect of the small surface metal particles in the perovskite solar cells. Figures
1(a) and 1(b) illustrate the schemes of the model for the plasmonic perovskite solar cell with
metal nanoparticles (Au or Ag) embedded in the perovskite absorber at front and rear
surfaces, respectively. The solar cell is built up based on the common perovskite solar cell
geometry (FTO: 700 nm, TiO2: 50 nm, Sprio-OmeTAD: 250 nm and Au back reflector: 60
nm). The thickness of the perovskite absorber is varied from 10 nm to 400 nm for the
investigation of the metal nanoparticle plasmonic effects on the solar cell performances. The
refractive index and the extinction coefficient of the perovskite absorber is measured using
ellipsometer as shown in Fig. 2(a), which corresponds well with the data in other publications
[21]. The optical constants of the other materials in the solar cells are taken from the reference
[22].

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1702
 To find out the optimum condition of the metal nanoparticles for a highest absorption
enhancement in the ultrathin perovskite absorber, the radius and the SC density of the
nanoparticles are systematically investigated. The thickness of the perovskite is selected to be
10 nm to demonstrate an ultrathin case. The radius of the metal nanoparticle is varied from 5
nm to 15 nm while the SC density is changed from 10% to 50%. Periodic boundary
conditions (PBCs) are used at the lateral boundaries of the simulation model to mimic the
infinite periodic arrays of nanoparticles. To quantify the influence of the nanoparticles on the
performance of perovskite solar cells, the absorbance of the perovskite absorber is first
calculated. Then by integrating the absorbance with the AM 1.5 solar spectrum, the area
independent JSC can be obtained, assuming that all generated electron-hole pairs contribute to
the photocurrent. Through mapping the perovskite absorption enhancement with nanoparticles
as a function of the particle radius and the SC density, the optimized condition for the highest
absorption enhancement in the perovskite absorber is achieved as shown in Figs. 2(b)-2(e).

Fig. 2. (a) The real and imaginary parts of the complex refractive index of the perovskite
material measured by ellipsometer. (b)-(e) Absorption enhancement with Au and Ag
nanoparticles at different positions in 10 nm thick perovskite layer as a function of the radius
and the SC density.

Through the comparison of the perovskite absorption enhancement with Au nanoparticles

in Figs. 2(b)-2(c) to that with Ag nanoparticles in Figs. 2(d)-2(e), the highest absorption
enhancement of 323% is obtained with the optimized Ag nanoparticles at the rear surface of
the solar cell with the particle radius of 10 nm and the SC density of 30%. The best position
of the integrated nanoparticles is found to be at the rear surface in the absorber thereby
avoiding the nanoparticle absorption loss when incorporated at the front surface, which can
also be confirmed from the absorbance curves in Fig. 3(a). The Ag nanoparticles integrated at
the rear surface can further boost the light absorbance in the short wavelength below 500 nm
compared with the case with Ag nanoparticles on top. From Figs. 2(b)-2(e), it can also be
observed that the Ag nanoparticles can enhance the absorbance more than the Au
nanoparticles. That is mainly due to a stronger plasmonic near field light concentration effect
from the Ag nanoparticle, which is illustrated in Figs. 3(b) and 3(c). From the comparison, it
is clear that light intensity of Ag nanoparticles is much stronger than that of Au nanoparticles
with the same size at the wavelength of 630 nm. The light energy is confined effectively
around the Ag nanoparticle near the plasmon resonance frequency thereby further improving
the light absorption of the perovskite material surrounding the nanoparticle.

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1703
 Fig. 3. (a) Absorbance in perovskite layer with/without Ag nanoparticles at the rear surface or
on the top surface. (b)-(c) Normalized light intensity around Au and Ag nanoparticle in solar
cells at the wavelength of 630 nm.

Based on the optimum condition of Ag nanoparticles in perovskite solar cells with thin
absorber for the enhanced light concentration effect, a lumpy Ag nanoparticle model is
designed with small Ag particles at a radius of 10 nm decorated on the surface of a large Ag
core particle. To optimize the lumpy nanoparticle model, we define the radius ratio α as the
ratio of the radius of the Ag core particle to that of the Ag surface particles and incorporate
the lumpy nanoparticles into the thin perovskite absorber at the rear surface as being shown in
Figs. 1(c) and 1(d). The radius ratios, α, are selected to be 75/10, 100/10 and 125/10 to find
out the best nanoparticle parameters for the highest absorption enhancement in solar cells.
Through the calculation of the absorption enhancement as a function of the radius ratio and
the SC density, we find that the highest absorption enhancement of 431% is obtained under
conditions with a radius ratio α = 100/10 and the SC density of 40%, as shown in Fig. 4(a).

Fig. 4. (a) Absorption enhancement mapping results in the perovskite layer with lumpy Ag
nanoparticles. (b) Light absorbance of the perovskite absorber with/without metal nanoparticles
at the optimized conditions.

To further illustrate the influence of the lumpy nanoparticle on the absorbance in the
perovskite layer, light absorbance curves of 10 nm thick absorbers integrated with small Au
particles, small Ag particles and lumpy Ag nanoparticles are plotted respectively and
compared with the flat reference case in Fig. 4(b). It can be found that with the small Au
particles in the perovskite layer, the absorbance in the longer wavelength region is improved
significantly due to the plasmonic light concentration effect while the light absorbance in the
same wavelength region can be further increased with the small Ag particles. In contrast, the
lumpy Ag nanoparticles can further boost the absorbance in the perovskite layer over the
entire wavelength region significantly. The improvement of perovskite film’s light absorbance
with lumpy nanoparticles can be ascribed to two possible reasons. One is that plasmonic light
scattering effect from the large core particle and light concentration effect from the small
surface particles being provided by lumpy Ag nanoparticles boost the longer wavelength light

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1704
absorption. The other one is that the perovskite nanoshell structure induced by the lumpy
nanoparticle shown in Fig. 1(d) can enhance the short wavelength absorbance due to the
modes coupling into the shell structure and the enlarged effective perovskite material
absorption area [23].
The achieved enormous absorption enhancement allows us to further investigate short
circuit currents of solar cells with different absorber thicknesses. Based on the previous
nanoparticle optimization results, JSC values in nanoparticle incorporated solar cells with
different thick perovskite layers (from 10 nm to 400 nm) are calculated and compared to the
flat reference solar cells as shown in Fig. 5.

Fig. 5. JSC of the perovskite solar cells with surface engineered metal nanoparticles as a
function of the perovskite absorber thickness.

It can be observed that the JSC enhancement is much higher when absorber is thinner.
When the thickness is below 100 nm, JSC can be dramatically improved with rear surface
engineered metal nanoparticles. CH3NH3PbI3 is proved to be a good light absorber with
visible light absorption coefficient of around 2.5 x 105 cm−1 [24], therefore, most visible light
is fully absorbed already when the film is thicker than 100 nm. This situation is more
significant in terms of the case with lumpy Ag nanoparticles. When the thickness of the
absorber is increased from 10 nm to 50 nm, the JSC values are improved from 3.44 mA/cm2
and 10.52 mA/cm2 without nanoparticles to 18.29 mA/cm2 and 22.5 mA/cm2 respectively
with lumpy nanoparticles. And after the rapid increase in JSC with respect to the absorber
thickness in this range, JSC tends to saturate at around 24.5 mA/cm2 with further increased
thicknesses. Rather than a dramatical improvement in JSC, further increasing the perovskite
layer thickness does not significantly improve the solar cell performance. In addition, the
solar cell performance with lumpy Ag nanoparticles outweighs that with small Ag and Au
particles, especially at the absorber thickness of less than 50 nm. In contrast, in terms of the
solar cells with small Ag particles at front, JSC decreases with increasing the thickness to over
200 nm compared to the flat reference case. This is mainly due to that the absorption loss
from nanoparticles overweighs the nanoparticle induced absorption gain in the absorber.
These findings indicate a preferable absorber thickness choice with designed lumpy
nanoparticles for high performance ultrathin solar cells. At the point of the 50 nm thick
perovskite layer, JSC is increased from 10.52 mA/cm2 to 22.5 mA/cm2, which is even higher
than the maximum achievable Jsc value in a flat 300 nm thick perovskite solar cell (21.6
mA/cm2).
3. Conclusion
In conclusion, it has been theoretically found that the radii of the core and the surface particles
and the surface coverage density of the lumpy Ag nanoparticles play an imperative role in the

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1705
light absorption enhancement of ultra-thin perovskite solar cells. A maximum short circuit
current density (JSC) gain of 431% relative to the reference flat perovskite solar cell with the
absorber layer thickness of 10 nm can be achieved through optimizing the lumpy Ag
nanoparticles. Under the optimized condition, we have found that the solar energy absorbed
by a 50 nm thick perovskite layer is even higher than that for a 300 nm thick perovskite
absorber without the modified nanoparticles.
Acknowledgments
Min Gu thanks the Australian Research Council for its support (DP140100849) and also
acknowledges support from the Science and Industry Endowment Fund. Yong Peng
acknowledges the support of the Australian Centre for Advanced Photovoltaics.

#251132 Received 30 Sep 2015; revised 29 Oct 2015; accepted 3 Nov 2015; published 12 Nov 2015
© 2015 OSA 14 Dec 2015 | Vol. 23, No. 25 | DOI:10.1364/OE.23.0A1700 | OPTICS EXPRESS A1706