Light: Science & Applications (2014) 3, e161; doi:10.1038/lsa.2014.

42
OPEN ß 2014 CIOMP. All rights reserved 2047-7538/14
www.nature.com/lsa

REVIEW

Metallic nanostructures for light trapping in

energy-harvesting devices
Chuan Fei Guo1, Tianyi Sun1, Feng Cao1, Qian Liu2 and Zhifeng Ren1

Solar energy is abundant and environmentally friendly. Light trapping in solar-energy-harvesting devices or structures is of critical
importance. This article reviews light trapping with metallic nanostructures for thin film solar cells and selective solar absorbers. The
metallic nanostructures can either be used in reducing material thickness and device cost or in improving light absorbance and thereby
improving conversion efficiency. The metallic nanostructures can contribute to light trapping by scattering and increasing the path
length of light, by generating strong electromagnetic field in the active layer, or by multiple reflections/absorptions. We have also
discussed the adverse effect of metallic nanostructures and how to solve these problems and take full advantage of the light-trapping
effect.
Light: Science & Applications (2014) 3, e161; doi:10.1038/lsa.2014.42; published online 25 April 2014

Keywords: conversion efficiency; light trapping; photovoltaics; plasmonics; solar absorber

INTRODUCTION has not received enough attention. Solar thermal devices can absorb
The conversion of solar energy to electricity or heat might be the light from ultraviolet to near infrared (IR) (0.3–2 mm), which is much
ultimate means to help solve the energy crisis when hydrocarbon broader than the wavelength that any single-junction solar cells can
resources such as coal and other fossil fuels cannot satisfy the energy absorb (Figure 1). The conversion efficiency of solar thermal devices
demand. Solar energy is abundant, ,5000 times our current power (such as solar water heaters) is also much higher; for example, an
consumption.1 The use of solar energy can also reduce the envir- evacuated tube collector can have an efficiency of approximately
onmental problems caused by the consumption of fossil fuels by reduc- 80% in the summer. Such solar water heaters have been widely used
ing dusts, noxious gases and greenhouse gases, as well as the resulting in China and Europe and are quite effective in CO2 reduction.2
haze, acid rain and global warming. To date, the worldwide installed
capacity of solar harvesting devices is ,60 GW in electric energy and PLASMONICS FOR LIGHT TRAPPING IN PHOTOVOLTAICS
,300 GW in thermal energy,2 with an annual rapid increase. For the Photovoltaic devices can covert solar energy into electricity.
existing technology, there is room for further improvement by either Commercial crystalline silicon (c-Si) solar cell technologies often
enhancing the light absorption or avoiding loss of electricity or heat adopt a basic etching process to produce pyramids to reflect light back
after absorption. Recently, new advances in nanotechnology and into silicon and hence improve the absorbance. A silicon nitride layer
material fabrication methods have resulted in an emerging field of is then applied onto the pyramids to act both as a passivation layer and
plasmonics by properly introducing metallic nanostructures to manip- as an antireflective coating (ARC). The MA Green group at the
ulate light, enabling light trapping in active layers and thereby enhan- University of New South Wales has performed important pioneering
cing the performance of energy-harvesting devices.3 In addition, work on thick Si solar cells. This group achieved an efficiency of ,25%
certain highly absorbing surfaces or structures with broadband absorp- for single c-Si solar cells4,5 and 19.8% for polycrystalline Si solar cells
tion promising to extend the working wavelength of the solar energy using the light-trapping structures of inverted pyramids and a hon-
spectrum (Figure 1) have been realized. The light-trapping effect, how- eycomb structure,5 respectively. However, c-Si is not a highly absorb-
ever, allows the thickness of materials and the costs of solar cells to ing material and requires a thickness of .100 mm to enable nearly
decrease, which in turn benefits electricity collection when the minor complete light absorption. While, too thick of a material is not good
carrier diffusion length in the active layer is not sufficiently long. for electricity collection because the thickness must be at least several
In this review, we focus on light trapping induced by metallic nano- times smaller than the minority carrier diffusion length. Reducing the
structures for solar energy collection. Corresponding applications are thickness of the active layer can therefore reduce the recombination of
not only for photovoltaics, but also for solar thermal. In fact, solar carriers and improve the conversion efficiency. By contrast, thin film
thermal has a market with profit even higher than photovoltaics, yet solar cells, which use highly absorbing materials such as amorphous
1
Department of Physics and TcSUH, University of Houston, Houston, TX 77204, USA and 2National Center for Nanoscience and Technology of China, Beijing 100190, China
Correspondence: Professor Q Liu, National Center for Nanoscience and Technology of China, No. 11 Beiyitiao Zhongguancun, Beijing 100190, China
E-mail: liuq@nanoctr.cn
Or Professor ZF Ren, Department of Physics and TcSUH, University of Houston, Houston, TX 77204, USA
E-mail: zren@uh.edu
Received 22 September 2013; revised 4 November 2013; accepted 15 November 2013
 Solar energy
CF Guo et al
2

photovoltaic absorber layer can couple sunlight into surface plasmo-

Solar absorber
nic polariton (SPP) modes that are supported at the semiconductor/
metal interface (Figure 2c). Light in the propagating waveguide mode
is absorbed in the plane of the semiconductor, while carrier collection
occurs out of plane, allowing for a reduction in overall thickness.8
GaAs solar cell (28.3%)

Efficiency
Scattering effect of metallic nanoparticles for light trapping
C-Si solar cell (25%) There have been many experiments that prove the light trapping of
metal nanoparticles utilizing the scattering effect. In 2005, Yu and co-
workers9 deposited Au nanoparticles on a thick Si p–n junction diode;
Dye-sensitized solar cell (11%)
they observed enhancement of optical absorption and photocurrent
via the excitation of surface plasmon resonances in spherical Au nano-
A-Si:H solar cell (10.1%) particles. In fact, early in 1998, Stuart and co-workers10 utilized metal-
lic nanoparticle for improved photodetectors. And in photovoltaic
applications, Yu et al.11 also observed that metal nanoparticles with
0.5 1.0 1.5 2.0 2.5 mm a modest density could lead to an efficiency enhancement of 8.3%
(corresponding power output increases from 2.77 to 3.00 mW cm22)
Figure 1 Solar spectrum and the working wavelength and comparison of effi- in an amorphous Si thin cell for which the active layer was only 240 nm
ciency for various solar-energy-harvesting mechanisms. A-Si, amorphous silicon; thick. Green et al.12 investigated the light-trapping effect using Ag
C-Si, crystalline silicon. nanoparticles on a 1.25-mm-thick c-Si on an insulator solar cell and
reported a broadband enhancement and a 16-fold enhancement at
silicon (a-Si), GaAs and CuInxGa12xSe2, require a film thickness of only 1050 nm. Atwater et al.13 demonstrated that GaAs thin cells exhibit
hundreds of nanometers to microns. Thin film solar cell technologies an improvement of 8% for the short circuit current density with
can largely reduce the use of semiconducting materials and the cost. In templated high aspect-ratio Ag nanoparticles, and these nanoparticles
addition, thin films can be easily deposited onto many inexpensive not only scatter light, but also decrease the top contact sheet resistance.
substrates including glass, metals, or polymers. If the active layer can The thin cells with Ag nanoparticles yield a significant enhancement
be further reduced to ,10 nm, the semiconductors, especially those are for wavelengths longer than 600 nm (Figure 3).13 When using a peri-
properly patterned, will be extremely flexible6 such that they can be used odic array of metal nanoparticles for light trapping, the grating pitch
in flexible solar cells, which might act as the power source for electronic should be selected to allow higher order diffraction modes for long
skins and foldable photoelectronics.7 The main problem for thin film wavelengths while maintaining the highest possible fill factor. For
solar cells is that the materials exhibit very small absorbance of near- example, a set of optimal parameters for light trapping in Si solar cells
bandgap light, and reducing the thickness will further cause a significant is a particle size of ,200 nm and a pitch of ,400 nm.14
loss of absorption, therefore leading to a limited efficiency. The particle shape, size, distance from the semiconductor and
The emerging area of plasmonics offers new paths for improving the refractive index of the medium could all affect the coupling effi-
efficiency of thin solar cells. There are three extensively investigated ciency.3,11,15–17 Nanospheres are the most commonly used scattering
plasmonic structures integrated in thin cells that can remarkably centers. Figure 4a and 4b show the normalized scattering cross section
decrease the thickness of photovoltaic materials while maintaining of spherical particles as a function of wavelength and particle size in
good absorbance,3,8 as shown in Figure 2. First, metallic nanoparticles both air and Si.17 The plasmonic resonance exhibits an obvious red-
on top of a solar cell can scatter a broad range of sunlight to couple and shift effect in silicon (which has a higher refractive index compared
trap freely propagating plane waves in the thin film by folding the light with air). In addition, the resonance peaks redshift and broaden with
into a thin absorber layer (Figure 2a). In this case, the angular redis- increasing particle sizes. This redshift significantly enhances the light
tribution of the scattered light and back contact reflection also increase trapping in the red and near-IR region, which is otherwise a low
the optical path length and therefore, contribute to light trapping. absorption region for Si. Typically, particles with a size of ,100 nm
Second, embedded metallic nanoparticles can be used as subwave- can provide the highest scattering efficiency. Particle shape should also
length antennas for which the excited localized surface plasmons couple be considered. Cylindrical and hemispherical particles exhibit higher
with the semiconductor, increasing its effective absorption cross- path length enhancements than spherical particles.3,15,16 This effect is
section (Figure 2b). Third, a patterned metallic back contact of a thin evidenced in Figure 4c, which reveals the difference in fraction of light

a b c

Figure 2 Three methods that utilize metallic plasmonic nanostructures for light trapping in thin solar cells. (a) Scattering effect and angular redistribution of the
scattered light with metallic nanoparticles on top of a cell. (b) Near-field effect of embedded metallic nanoparticles. (c) Coupling sunlight into SPPs with metallic
nanostructures on the rear contact. Blue: ARC; orange: active layer; gray: metal. Figure reproduced with permission from Ref. 3, ß 2010 Macmillan Publishers Ltd.
ARC, antireflective coating; SPP, surface plasmonic polariton.

Light: Science & Applications doi:10.1038/lsa.2014.42

 Solar energy
CF Guo et al
3

Au
a p-GaAs 5×1018 cm–3
b
200 nm
Cap 300 nm
Window 30 nm p-Al0.8Ga0.2As 1×1018 cm–3
Emitter 50 nm p-GaAs 4×1018 cm–3
Base 150 nm n-GaAs 2×1017 cm–3
BSF 500 nm n-Al0.8Ga0.2As 2×1018 cm–3
Buffer 1 mm n-GaAs 2×1018 cm–3
0.5 mm
Substrate 350 mm n-GaAs 1×1018 cm–3

200 nm Au

Normalized external quantum efficiency

c d
15 3
Current density (mA cm–2)

DL DL
SL SL
DH DH
10 2
SH SH
w/o

5 1

0 0
0 0.2 0.4 0.6 0.8 1.0 300 400 500 600 700 800 900 1000
Voltage (V) Wavelength (nm)

Figure 3 (a) The layered structure of a GaAs solar cell with Au nanoparticles on top. (b) Scanning electron microscopy (SEM) image of densely formed high aspect-ratio
Au nanoparticles. (c) Photovoltaic I–V curves for the GaAs solar cells under AM 1.5 illumination. (d) Normalized spectral responses for the GaAs solar cells. A solar cell
without Ag nanoparticles (w/o) on top was used as a reference. Figure reproduced with permission from Ref. 13, ß 2008 AIP. AM, air mass; BSF, black surface field;
DH, densely formed high nanoparticles (3.33109 cm22 density/220 nm height); DL, densely formed low nanoparticles (3.33109 cm22 density/55 nm height); SH,
sparsely formed high nanoparticles (1.83109 cm22 density/220 nm height); SL, sparsely formed high particles (1.83109 cm22 density/55 nm height).

scattered into semiconductor substrates with nanocylinder, hemisphere, often mixed with or embedded in active materials such that the sur-
sphere and large sphere (scattered light decreases with the same order). rounding active materials can become highly absorbed due to the high
However, nanospheres can be easily synthesized such that they are still density of states of the phonons and the fact that the nanoparticles can
widely used. Figure 4d shows that for a point dipole, the fraction of light directly excite charge carriers. Considering the fabrication method,
scattered into a semiconductor substrate decreases with increasing dis- this mechanism is especially suitable for preparing dye-sensitized solar
tance to the underlying Si substrate. However, the decrease is not dra- cells using solution processes.20 The small particle size and close par-
matic; for example, the fraction of light is 84% when the dipole is 60 nm ticle-to-particle spacing often help to further enhance the near-field
away from the substrate.16 It is often not recommended that the nano- effect; however, the small nanoparticles do not exhibit a great scatter-
particles be placed directly on the active layer, as this placement causes a ing effect.3 This near-field mechanism works well for materials in
carrier recombination problem. In fact, the effective scattering cross- which the carrier diffusion lengths are small, and photocarriers must
section can be increased by increasing the distance between the nanopar- thus be generated near the collection junction area. The absorption
ticles and the substrate, as this distance prevents destructive interference rate in the semiconductor must be larger than the reciprocal of the
effects between the incident and reflected fields, although it comprises the typical plasmon decay time to avoid dissipation of the absorbed energy
near-field coupling.3,17 The interference problem can also be solved by into ohmic damping in the metal.3 The optical thickness of organic
placing the nanoparticles on the rear of the solar cells. In this case, short thin films is typically larger than the carrier diffusion length, thus
wavelength light can be largely absorbed by the semiconducting materials, reducing the thickness while maintaining the absorbance in organic
while long wavelength light, e.g., IR and red light that reaches the rear of solar cells is significant. Embedded nanoparticles of Ag could effi-
the cell can be scattered by the nanoparticles and be trapped.18 In addi- ciently increase the light absorption in ultrathin organic solar cells
tion, Ag is a better metal than Au as Ag particles yield much higher path and thereby improve the efficiency.21 By incorporating electrodepos-
length enhancements than Au particles15 and offer a lower price. In ited 13 nm Ag nanoparticles on surface-modified transparent electro-
addition to metal nanoparticles, other structures such as gratings with des, the efficiency of organic solar cells could increase from 3.05% to
ARC could also result in absorption enhancement in ultrathin solar cells 3.69% because of the improved absorbance via the strongly enhanced
due to improved coupling to guided modes.19 local electromagnetic field in the vicinity of the Ag nanoparticles.22 Au
nanoparticles could also lead to an efficiency improvement in polymer
Near-field effect of metallic nanoparticles in solar cells bulk heterojunction solar cells.23,24 However, metal nanoparticles may
Another method for light trapping is to make use of the strong local also degrade the carrier mobility and thus compromise the benefit of
field of very small metallic nanoparticles. Metallic nanoparticles are the near-field enhancement.25 Enhanced efficiency or photocurrent

doi:10.1038/lsa.2014.42 Light: Science & Applications

 Solar energy
CF Guo et al
4

a b
Normalized scattering cross section

Normalized scattering cross section

50nm ln air
8 ln Si (n=3.5)
30 20nm

6
20
4
50nm
200nm
2 10
100nm
20nm 100nm 200nm
0 0

300 400 500 600 700 800 900 1000 1100 1200 300 400 500 600 700 800 900 1000 1100 1200
Wavelength (nm) Wavelength (nm)
c 1 d
1
Fraction scattered into substrate

Fraction scattered into substrate

0.8 0.8 fsubs/(fsubs+fair)

0.6 0.6

0.4 Dipole 0.4

Cylinder
Hemisphere
0.2 Sphere 100 nm 0.2
Sphere 150 nm

0 0
500 550 600 650 700 750 800 0 20 40 60 80
Wavelength (nm) Distance from substrate (nm)

Figure 4 The effect of metallic particle size, shape, distance to substrate and refractive index of medium for nanoparticle scattering. (a, b) Normalized scattering cross
sections of Ag nanoparticles in air and Si with various sizes. (c) Fraction of light scattered into the substrate for various sizes and shapes of Ag particles on Si; the dipole is
10 nm away from Si. (d) Fraction of light scattered into Si as a function of distance for a point dipole above a Si substrate. Figure reproduced with permission: a, b, Ref.
17, ß 2010 Elsevier; c, Ref. 3, ß Macmillan Publishers Ltd; d, Ref. 16, ß 2008 OSA.

with the plasmon near-field coupling of nanoparticles has also been active layers. Green et al.33 noted that although metal absorption occurs,
observed in inorganic solar cells including n-CdSe/p-Si heterojunc- this process does not fully compromise the benefit of light trapping in
tion diodes26 and dye-sensitized solar cells.20,27–30 In dye-sensitized the active layer in standard systems, especially organic solar cells. The
solar cells, it is also necessary to consider the negative effects (e.g., fabrication of structures with SPPs modes are typically gratings or
charging) of the metal nanoparticles in addition to the localized sur- grooves in the rear contact, and the active layer should directly contact
face plasmon effects.31 This field has been quite attractive with the the metallic nanostructures. For example, Ferry et al.34 demonstrated
development of synthesis processes of metal nanoparticles and assem- that metal contact with a single 100 nm wide groove covered by a
bly technologies. 200 nm Si thin film can enhance absorption by a factor of 2.5 over a
Note that for some active materials, the near-field mechanism may 10 mm area for the portion of the solar spectrum near the Si bandgap.
not work. For example, a-Si does not benefit from the resonance of Ag When using arrays of Ag nanoridges, a large grating pitch (6 mm) results
nanoparticles due to the mismatch between the bandgap of a-Si and in an enhancement similar to the single ridge case because strong inter-
the near-field resonance frequency; for c-Si, the global absorption may ference does not occur between the SPP waves, whereas a small pitch of
not benefit from the local enhanced field due to the weak absorbance of 300 nm leads to a higher absorption enhancement that is more sensitive
c-Si and the Ohmic loss in the nanoparticles.32 Therefore, when uti- to wavelength, with narrower spectral features and a wider variation in
lizing the near-field effect, we must carefully select the materials, metal enhancement across the spectral range.35 The largest enhancement
nanoparticle size, shape, position, etc. to ensure that the enhanced could achieve 25 in a narrow wavelength range. SPPs can be excited
absorption in the active layer can compensate for the accompanying only for transverse magnetic polarized light incident on the rear grat-
negative effects (e.g., absorption in metal, loss of carrier mobility, ings and not for transverse electric (TE) polarized incident light.35
increased cost, etc.). Wang et al.36 demonstrated that a-Si on hybrid gratings of Ag and
indium tin oxide (ITO) exhibits broadband light absorption enhance-
SPPs induced absorption enhancement ment, which is related to Fabry–Pérot (F–P) resonance, SPP resonance
SPPs are plasmon modes that propagate along the metal/dielectric and planar waveguide coupling. If a thick dielectric spacer layer is
interface. The SPPs can propagate along the interface for a relatively placed between the metallic gratings and the active layer, light trap-
long distance, but are confined to the subwavelength scale in the per- ping still occurs, but the enhancement is due to the local and guided
pendicular direction. This evanescent wave decay occurs faster in metals modes rather than the SPP modes.37,38 Such textured structure with a
than in dielectric materials, which is beneficial for light absorption in spacer is also promising; for example, self-cleaning nanodome solar

Light: Science & Applications doi:10.1038/lsa.2014.42

 Solar energy
CF Guo et al
5

cells with a 280-nm-thick hydrogenated a-Si:H layer can absorb 94% odd multiples of l/4n (l is the incident wavelength and n is the
of the light with wavelengths of 400–800 nm, which is significantly refractive index), the beams reflected from the two interfaces have a
higher than the 65% absorption of flat film devices.39 phase difference of p. Thus, reflection at l is greatly reduced and
The enhancement with arrays of ridges is reminiscent of surface transmission is accordingly greatly enhanced. At wavelengths other
wrinkles and folds,40–42 which are spontaneously generated by depos- than l, a high reflection can be observed. This type of structure is
iting a metallic film on an elastomeric substrate followed by heating. often referred to as a transmission filter in early papers.44,45 One vari-
Here, the elastomeric layer can be the organic active materials, and the ation of such FP interferometers is the reflection filter: the exit thin
metallic wrinkles or folds will act as the nanostructured back contact metal layer is replaced by an opaque metal mirror (Figure 6). The
(Figure 5). The folds might be more efficient than wrinkles because the reflection filter also exhibits a selective reflection property, for which
structures are sharper. The grating structures prepared using conven- a low reflection at l and high reflection at wavelengths other than l are
tional nanofabrication methods on the back contact help to enhance observed.44,45
the absorption; however, this enhancement comes at a price. Surface
wrinkling or folding on the back contact might solve this problem for Metamaterials
organic solar cells in a cost-effective manner. In addition, organic
Photonic metamaterials are artificially constructed structures com-
active materials used in these novel structures yield even better absorp-
posed of subwavelength building blocks with micro- or nano-
tion than Si in the near field.33
structures. The emergence of metamaterials was originally inspired
by the discoveries of very low-frequency effective plasmons of thin
ABSORPTION BY METAL/INSULATOR/METAL (MIM)
metallic wire grids46 and the effective negative permeability of split
MULTILAYERED STRUCTURES
ring resonators.47 Guided by the theoretical and experimental success
Another family of important metallic structures for light absorption is
of the effective medium theory,48 the field has rapidly developed in
MIM multilayered systems. Thanks to the advancement of nanotech-
recent years. Many fascinating optical properties and corresponding
nology, especially in nanofabrication, there has recently been signifi-
devices or structures have been realized, including an invisibility cloak,
cant progress in the development of conventional MIM structures,
perfect absorber and superlens.49–51 There have been many excellent
which offer different fascinating properties. Since the appearance of
reviews on the subject,52–55 but here we focus only on those related
metamaterials approximately one and half decades ago, metal pattern/
MIM structures.
insulator/metal multilayered structures have begun to play an impor-
tant role in the field. From the electromagnetic viewpoint, a collection of objects whose
size and spacing are much smaller than the wavelength can be
FP MIM interferometer described by an effective permittivity e and permeability m.53 One very
The FP interferometer (etalon) was invented in 1897 43 and typically important family of metamaterials is the MIM structure.50,56,57 The
consists of a transparent plate with two highly-reflecting surfaces (usu- schematic unit cells of one such example are presented in the Figure 7.
ally made of semitransparent metal), forming a MIM structure. The structure consists of two metallic elements: a top metallic nano-
Similar to a conventional ARC, the FP interferometer utilizes the pattern and a bottom ground plane, with an insulating dielectric layer
destructive interference between the reflected waves from the air/metal as the spacer. The metal patterns are a type of electric ring res-
and insulator/metal interfaces. When the thickness of the insulator is onator49,58 and couple strongly to uniform electric fields but negligibly
to magnetic fields. It was first observed in Ref. 58 that when paired to
the dielectric layer and bottom metallic layer, the magnetic compo-
a ARC nent of light couples to both the center section of electric ring resonator
Active layer SPPs patterns and the ground plane, generating antiparallel currents, which
results in the resonant response. Thus, by changing only the thickness
Metal of the insulating layer, not the geometry of the pattern arrays, the
Nanoridges magnetic response m can be tuned independent of the electric response
e. When the geometry of the entire system is so tuned that e(l)5m(l) is
b satisfied, a high absorption at the wavelength l can be achieved.
ARC
However, because the electromagnetic response is resonant in a narrow
Organic active layer band, broadband application is quite limited. Some attempts were
made, most of which were realized by combining several resonances
into one desired frequency range or complex pattern designs.59,60 For
Surface wrinkles
example, Aydin et al.60 described an Ag nanopattern (100 nm)/SiO2

c ARC

Organic active layer Air

Metal

Surface folds Dielectric

Metal
Figure 5 (a) Nanoridges prepared by conventional nanofabrication for light
trapping. (b, c) Two proposed structures using spontaneous wrinkling and folding
for preparing a patterned back contact. Compared with wrinkles, folds (which are
much sharper) may lead to higher enhancement. Wrinkles can convert to folds at
large strains. ARC, antireflective coating; SPP, surface plasmonic polariton. Figure 6 A schematic side view of an MIM structure. MIM, metal/insulator/metal.

doi:10.1038/lsa.2014.42 Light: Science & Applications

 Solar energy
CF Guo et al
6

a b 1.0
Experimental
Wy

Absorbance
Wx d
h
t 0.5
a

0.0 H Sxz
1.0 E Sxz
FDTD

Absorbance
1.5

200 nm

0.0
1.0 1.5 2.0 2.5
Wavelength (mm)
1 mm

Figure 7 An example of an MIM metamaterial structure. (a) Schematic view and SEM image of the MIM structure and (b) corresponding absorptance. Figure
reproduced with permission from Ref. 56, ß 2010 AIP. FDTD, finite difference time domain; MIM, metal/insulator/metal; SEM, scanning electron microscopy.

(60 nm)/Ag film (100 nm) super absorber that exhibits an average phase factors. Most importantly, from the definition of Fresnel coeffi-
absorbance of 71% over the entire visible spectrum. cients, it can be observed that the phases of ~ri and ~ri=m are not limited
The application of these MIM types of metamaterials is closely to 0 or p, but depend on that of different n ~i . Under such circumstances, it
related to the development of nanofabrication techniques and is possible that ~ri ~{~ri=m e i2h can be satisfied at a thickness of d?l/4ni
advances of computational simulation. With the first demonstrations (2h?p). In extreme cases, if ~ri and ~ri=m are already out of phase, to satisfy
being realized in the range from microwaves to the far IR in the early the low reflection condition, d could be much smaller than l. As described
2000s,61,62 applications in visible and even close ultraviolet range have in Ref. 66, to achieve a low reflection of approximately 20% at 500 nm,
been easy to find in recent years.63,64 only 8 nm Ge is required on a Au film. Such ultrathin structures with high
absorptance are mostly desired for photovoltaic applications.
Absorptive material as the insulator
Both F–P MIM systems and the metamaterial MIM systems mentioned Dielectric/perforated metal film/insulator/metal (DPIM) structures
above can function as a single frequency absorber. However, there is vital In conventional F–P MIM filters, the spacer is usually a lossless dielec-
difference between the two mechanisms: absorption in the F–P MIM tric layer. By replacing the lossless material with an absorptive mate-
system is based on phase accumulation, requiring a dielectric spacer on rial, such as amorphous silicon in the visible range, a similar effect can
the order of l/4n; metamaterials, however, are based on electromagnetic be observed: the resonance occurs at a thickness much smaller than the
resonance, requiring a thickness of the dielectric layer d,,l. How to wavelength. This effect helps narrow the scale gap between the meta-
narrow this scale gap and bring the two systems together is an interesting material MIM scheme and the F–P MIM scheme.65 Wang et al.65
topic. In one recent scheme, it was demonstrated that if a high index demonstrated that a perforated metal film/absorptive insulator/metal
absorptive material is incorporated into the structure, enhanced absorp- (PIM) structure satisfies the MIM interference requirements discussed
tion can be achieved with a broad bandwidth.65–67 above. In this structure, the a-Si film is only 15 nm thick, and the top
As described in a classic optics book,68 the reflected electrical com- Ag checkerboard covers ,50% of the a-Si surface. Such a PIM multi-
ponents from an insulator/metal system can be expressed by the layer system made of a nanoscopically perforated metallic film and an
Fresnel coefficients of corresponding interfaces: if only the first two ultrathin absorber formed a metamaterial effective medium that exhi-
1{~ ni
partial waves reflected back into air are considered, ~ri ~ repre- bits negative refraction in the frequency range of interest. If such a
1z~ ni planar PIM structure is further capped with a dielectric interference
sents the Fresnel coefficient of the air/insulator interface and
~i {~
n nm film to tune the phase difference between waves reflected from the top
~ri=m ~ represents that of the insulator/metal interface (~ ni and bottom surfaces of the PIM structure, the structure can highly
~i z~
n nm
and n ~m are the complex refractive indices of the insulator and the absorb electromagnetic radiation in the entire visible range, as shown
metal). The combined reflected wave is in Figure 8. The absorptance of this structure is sensitive to the thick-
ness of a-Si, but insensitive to the period or feature size of the metallic
~r i z~r i=m e i2h nanostructures. The introduction of the self-complementary pattern
~r ~ ð1Þ
1z~r i ~r i=m e i2h removes the electrical resonance in the interested range. The same
effect was also observed in aperiodic perforated metallic films (e.g.,
where h52p/nil is the single-trip phase change in the dielectric layer. aperiodic structures in Refs. 69, 70), in which unlike plasmonic struc-
Thus, the reflectance R in terms of energy is j~r j2 . Using simple algebra, tures, no dependence of periodicity is even required. Simulations were
to achieve the lowest reflection (r50) in air, one needs ~ri ~{~ri=m e i2h . performed to demonstrate this idea. A 12-nm-thick a-Si on 60-nm Ag
Recently, it was specifically noted in Ref. 66 that if the dielectric med- structure capped with a layer of random metallic nanomesh followed
ium is absorptive, ~ri and ~ri=m are no longer real numbers and consist of by a 60-nm-thick SiO2 film exhibits quite good absorptance (Figure 8),

Light: Science & Applications doi:10.1038/lsa.2014.42

 Solar energy
CF Guo et al
7

1.0 Ð lmax ~?
lmin ~0 f½1{rðl,hÞB ðl,T Þgdl
et ðh,T Þ~ Ð lmax ~? ð3Þ
0.8 lmin ~0 B ðl,T Þdl
Simulated absorptance

where l is the wavelength, r(l,h) is the angular dependent (incident

55 nm ITO angle h) spectral reflectance, S(l) is the direct normal solar irradiance
0.6 (AM 1.5), B(l,T) is the blackbody spectral radiation and T is the
20 nm
Ag
15 nm a-Si 50 nm
absolute temperature.
Solar water heater systems that apply a solar absorber to heat water
0.4
have been widely used in China and Europe. Such systems can be
DPIM with silver checkerboard pattern
Silver back reflector highly efficient; for example, a commercial evacuated tube collector
0.2 A-Si layer can achieve an efficiency of ,80%. However, for electricity genera-
Silver checkerboard pattern tion, the efficiency is much lower. A recent advance in solar ther-
DPIM with aperiodic perforated gold pattern
moelectric generators, in which a selective solar absorber absorbed
0.0 light and generated heat, while a pair of thermoelectric elements con-
300 400 500 600 700 800 nected to the solar absorber were used to convert the thermal energy to
Wavelength (nm) electricity (Figure 9), presented a peak efficiency of 4.6% under AM
1.5G condition.74 New designs of a CSP system might further enhance
Figure 8 Absorptance of DPIM structure with periodic and aperiodic structures. the entire conversion efficiency to 10%, which is comparable to a-Si:H
A schematic view of the DPIM structure is shown in the inset. A-Si, amorphous cells, with the greatest advantage being that such a system could pro-
silicon; DPIM, dielectric/perforated meta film/insulator/metal structures.
vide electricity around the clock by storing the heat, eliminating the
need of a battery for electricity storage. However, improving the effi-
ciency requires a large temperature difference between the two ends of
quite close to the result with a periodic structure. This result confirms the thermoelectric elements. A recent study reported that at an emit-
that the broadband absorption feature does not depend on specific tance of 0.05 and a solar concentration 10 times the AM 1.5G spec-
perforation geometry, or even aperiodicity; thus, it is possible to fab- trum, the optimal transition wavelength is observed to be 1.28 mm and
ricate highly absorbed PIM structures with simple and cost-effective have a 957 K equilibrium temperature.77 Therefore, good thermal
nanofabrication methods. stability at high temperatures is required.
Compared with the nanoparticle plasmonic photovoltaic structures, The high absorptance and low emittance can result in a high photo-
the dielectric/perforated meta film/insulator/metal (DPIM) structures thermal conversion efficiency of solar selective coatings. An ideal solar
have an ultrathin a-Si layer of ,10 nm thick, together with two absorber should have zero reflectance over the solar spectrum and zero
metal surfaces, and thus are more likely to be used in ultrathin solar emittance in the middle IR region (Figure 10), which allows complete
cells. The perforated top patterns can be used as the front contact absorption of solar energy without thermal radiation. However, in
with good flexibility and good electrical conductivity;70–72 therefore, reality, such an absorber does not exist; absorbers with 95% absorp-
the DPIM structure is potentially a good selection for flexible solar cells. tion and 5% emittance are realistic. The first practically useful coatings
were proposed by Tabor in 1955.78 Then, various spectrally selective
METALLIC NANOSTRUCTURE-ENABLED SELECTIVE SOLAR surfaces, such as black chrome coatings, Ni–Al2O3 cermet-based sur-
ABSORBER faces, Cr/CrxOy/Cr2O3 multilayer absorber coatings and paints includ-
Although much less attention is paid to solar thermal conversion pro- ing organic black carbon and inorganic pigment FeMnCuOx, were
cesses than photovoltaics, these processes are actually a major route for extensively investigated.78–84 According to the film configuration
harvesting solar radiation by converting sunlight directly to heat with and absorption mechanism, solar absorbers can be categorized into
the use of spectrally selective solar absorbers. The generated heat can six types.75 Among these types, most of the practically useful absor-
further be converted into electricity. The sunlight can be concentrated bers, including multilayer absorbers, cermet-based absorbers and tex-
to get a higher temperature and thereby a higher efficiency, known as tured surfaces, have metallic nanostructures. The metal component,
concentrated solar power (CSP) plant technology. There is ,300 GW particle size, orientation, coating thickness and metal volume fraction
of installed solar hot water system and ,3 GW of CSP plant world- in the matrix have a strong effect on the solar selectivity.
wide2,73 which is much larger than the installed capacity of solar pho- In solar selective coatings with metallic nanostructures, metals play
tovoltaic cells. New technologies of solar thermoelectric generators an important role. First, a thick bottom metal layer is used as an IR
and solar thermophotovoltaics for CSP plants are currently being reflector due to its low emissivity in the mid- and far-IR range and its
researched, but are not yet commercialized.74 A selective solar absorber high thermal conductivity. Most of the commercialized spectrally
that meets the requirements of the CSP program should have an selective coatings are supported on copper or aluminum substrates
absorptance of at least 0.95 and an emittance of less than 0.10 at 400 6C.75 to maximize the photothermal conversion efficiency. In addition to
The photothermal conversion efficiency can be determined by the the thick metal layer, metallic nanostructures, such as thin metal films,
metal nanoparticles and metal islands, are often employed in solar
solar selectivity of the solar selective absorber, which is determined by
selective surfaces. The thin metal film (several nanometers) is used
the absorptance (as) and emittance (et) of spectrally selective coatings
as a semitransparent reflective layer in multilayer absorbers. The metal
based on the following equations:76
nanoparticles embedded in a dielectric matrix are used to adjust the
Ð lmax ~? optical properties of the cermet layer. Metallic nanostructures, how-
lmin ~0 f½1{rðl,hÞS ðlÞgdl
as ðhÞ~ Ð lmax ~? ð2Þ ever, may cause some durability problems at high temperature. Here,
lmin ~0 S ðlÞdl we focus only on multilayer absorbers and cermet-based absorbers to

doi:10.1038/lsa.2014.42 Light: Science & Applications

 Solar energy
CF Guo et al
8

Glass vacuum enclosure Wavelength-selective

Electrical solar absorber
contact Thermoelectric
element

Cold side

Load

b c
Sunlight

Heat flow

Solar absorber/ Thermoelectric elements

thermal concentrator

Figure 9 (a) The structure of a solar thermoelectric generator consisting of a pair of p- and n-type thermoelectric elements, a flat-panel selective absorber that also acts
as a thermal concentrator. The device is surrounded by a glass enclosure that maintains an evacuated environment. (b) Optical image of the solar absorber used in the
device. (c) Illustration of thermal concentration. Figure reproduced with permission: Ref. 74, ß 2011 Macmillan Publishers Ltd.

discuss the function of metallic nanostructures in multilayer and cer- and is slightly less reflective in the visible region. The top dielectric
met coating solar absorbers using several examples. layer (C) acts as an ACR for the metal layer (D) and reduces the visible
reflectance. The thickness of this dielectric layer determines the shape
Multilayer absorbers and position of the reflectance curve. Another dielectric/metal (A/B)
Multilayer absorbers consist of alternating metal and dielectric layers. bilayer further reduces the reflectance in the visible region and broad-
The absorption mechanism of multilayer absorbers uses the multiple ens the absorption region (Figure 11a).75 The thickness of the dielec-
reflections at the layer interfaces. A bottom semitransparent metal tric layer has a large effect on the solar selectivity. The stability of this
layer (D) serves as a reflective layer that separates the two quarter- type of solar absorber strongly depends on the materials used. Metallic
wave dielectric layers. This layer has high reflectance in the IR region nanofilms with high melting points, high nitriding or oxidation re-
sistance and low diffusion are promising candidates.
The thermal emission of a one-dimensional metallodielectric peri-
1.6 1.0
odic structure was analyzed by Narayanaswamy and Chen.85 Their
Solar spectrum Blackbody radiation at 350 oC
1.4 simulation indicated that the emissivity of the periodic structure con-
Spectral power (W m–2 nm–1)

0.8 sisting of 11 unit cells with 10 nm silver and 150 nm of vacuum in the
1.2 IR range could be reduced by more than two orders of magnitude
1.0 compared with that of a bare 10-nm silver film. Several multilayer
Reflectance

0.6 absorbers based on different metallic nanofilms (Al, Pt, Cr, Ti) and
0.8
a b
0.6 0.4 A ARC
B Metal nanofilm
0.4 Metal nanoparticles
C
0.2 Cermet
0.2 D
E IR reflector
0.0
0.0
1 10
Wavelength (mm)
Figure 11 Two types of spectrally selective solar absorbers with metallic nano-
Figure 10 An ideal solar absorber with a sharp reflectance increasing from 0 to 1 structures. (a) Multilayered absorber. (b) Cermet solar absorber. ARC, antire-
at ,1.8 mm. flective coating; IR, infrared.

Light: Science & Applications doi:10.1038/lsa.2014.42

 Solar energy
CF Guo et al
9

dielectric layers (Al2O3, AlN, Cr2O3, SiO2) were developed for solar solar absorptance was increased while keeping the thermal emittance
thermal conversion application. In 2009, Barshilia demonstrated that unchanged.93 Other metals such as Co, Ti, Mo, W and Pt were also
AlxOy/Al/AlxOy multilayer absorbers exhibit a high absorptance of used as the metal component in Al2O3-based cermet. Although the
0.95–0.97 and a low emittance ranging from 0.06 to 0.08 at 82 6C.86 Mo–Al2O3 and W–Al2O3 cermets were expected to be suitable for
This coating on a Cu substrate was stable at up to 400 6C in air, and high-temperature application, difficulties still occurred because dif-
degradation occurred when the temperature exceeded 450 6C due to fusion or a phase change of the metallic nanoparticles at high temper-
the diffusion of Cu. Replacing Cu with a Mo substrate, the solar ature results in degradation of the coatings.94,95
absorber was stable up to 450 6C in air and 800 6C in vacuum.86 Double-layered coatings were also developed. In a double-layered
Other systems such as AlxOy/Pt/AlxOy,87 SiO2/Ti/SiO2/Al,88 AlN/Ti/ cermet film, solar radiation is absorbed internally through phase inter-
AlN,89 and HfOx/Mo/HfO2 were also investigated.90 The colored solar ference in double-cermet solar coatings. Simulations indicated that
selective coatings in the Ti/AlN multilayer structure were obtained by the double layer cermet film exhibits a higher conversion efficiency
adjusting the layer number and thickness.89 The prepared surfaces compared with the uniform cermet or graded cermet film.96 The
display black, purple, yellowish green, red and yellowish orange, double-cermet layer structure consisting of a AlN top layer, a cermet
among which the purple surface exhibited the best solar selectivity, layer with a low metal volume fraction, and another cermet layer with
with a high absorptance of 0.94 and a low emittance of 0.05.89 a high metal volume fraction exhibited a high solar absorptance of
Commercial solar absorbers often display a purple or blue color 0.953 and a near-normal emittance of 0.051 for W-AlN cermet97 and
instead of black; we should consider the light trapping not only in 0.933 and 0.025, respectively, for SS-AlN cermet.98 The W- and SS-
the visible region, but in the entire solar spectrum as well as emission AlN cermet films offer the advantage of the high reactivity of alumi-
in the IR region. HfO2 is a dielectric material with a high reflective num with nitrogen.97,98 The coatings with double absorption layers of
index, wide bandgap (5.5 eV) and good mechanical, chemical and high metal volume fraction and low metal volume fraction prepared
thermal stability. The HfOx/Mo/HfO2 system can be stable up to by co-evaporation exhibited a high absorptance of 0.911 and a low
500 6C in air. The HfO2 layer acted as an antireflection layer, and light emittance of 0.0196 at 50 6C.99 Double-layered cermet films are also
was largely absorbed in the HfOx and Mo layers. The addition of a Mo stable. For a SS-AlN cermet structure, only a small change was
layer between the Cu substrate and the HfOx layer could suppress the observed in the reflectance spectra after heating at 500 6C for 1 h.98
diffusion of Cu and thereby enhance the thermal stability.90 Generally, cermet-based solar absorbers exhibit good overall perfor-
mances of high absorptance, low emittance, and good thermal stability
Cermet-based solar absorbers and, therefore, have been used in CSP systems.75 Compared with mul-
Cermet is a metal–dielectric composite in which metal nanoparticles tilayer solar absorbers, cermet coatings may be prepared using cost-
are imbedded in the dielectric matrix. The coatings strongly absorb effective chemical solution approaches, although vacuum deposition
solar light due to inter-band transitions in the metal in combination such as sputtering remains the mainstream preparation method.
with small particle resonance, while the coatings are almost transpar-
ent in the IR region.75 The low emission mainly stems from the metal Novel design of solar absorbers
substrate, and the high absorbance is related to the cermet coating and Very recently, a work on a solution-processed plasmonic Ni nanochain–
the ARC. To date, cermet coatings have been extensively investigated Al2O3 cermet coating (Figure 12) revealed that unlike conventional mul-
for mid- and high-temperature solar thermal applications due to their tilayer graded-index cermet coatings, the SPP-enhanced solar absorption
high absorptance in a large solar region, low emittance in the IR region in these nanostructures is tailored by the lengths of the Ni nanochains
and good thermal stability. The solar selectivity of cermet-based solar instead of the cermet layer thicknesses, thus eliminating the requirement
absorbers can be affected by the coating thickness, metal volume frac- of costly vacuum deposition for stringent thickness control.100 This cer-
tion in the composites and particle size, shape and orientation. A met coating exhibited an absorption of .0.9 and an emittance of ,0.1.
typical and simple configuration comprises a metal layer for the IR In Figure 13, we propose a new structure of a selective solar absor-
reflector, a cermet layer and an antireflection coating, as illustrated in ber. The structure consists of a top metallic nanofilter, a middle
Figure 11b. The absorbing cermet coating may have an inherently absorbing layer, and a bottom metal substrate. The mesh size of the
high-temperature material layer of either a uniform or graded metal metallic nanofilter, w, can be optimized such that it is highly trans-
content or double layers with different metal contents. parent in the region where the absorbing layer works well (visible and
An early commercialized cermet solar absorber, black chrome (Cr– near-IR region) but highly reflective to light with a wavelength much
Cr2O3) prepared by electroplating demonstrated a solar selectivity larger than the mesh size (e.g., IR light .2 mm).101,102 With the
(ratio of absorptance to emittance) of 9.18.84 When the annealing development of nanotechnology, the top metal network structures
temperature increased to 400 6C, the amorphous Cr2O3 phase became are already available in a cost-effective manner,69,103 while the middle
crystallized, and the phase further evolved to Cr3O4 as the temperature absorbing layer can be sprayed graphite or other inexpensive materials
increased to 500 6C.91 Optimized coatings exhibited long-term with a modest thickness. Without a top metallic nanofilter, the emit-
stability, with the samples remaining stable after years of operation tance of the structure may reach a considerably high level, and hence,
at 300 6C in air. The graded Cr–Cr2O3 layers on Cu substrates exhibited the photo-thermal conversion efficiency is low.
a higher absorptance in the range of 0.90–0.94 and a lower emittance of
0.04.80 Al2O3 was then widely used as the dielectric material because of CONCLUSIONS AND OUTLOOK
its high thermal and chemical stability. Sputtered Ni–Al2O3 selective This article reviewed the applications of metallic nanostructures for
coatings were extensively investigated for mid- and high-temperature light trapping in solar energy-harvesting structures and devices from
applications. Ni–Al2O3 cermet-based solar selective surfaces were thin film photovoltaic cells to solar thermal structures and devices.
also prepared using other methods including dual-electron-beam The light trapping effect with metallic nanoparticles in photovoltaic
evaporation and a solution-chemical method.83,92 The solar selectivity devices can stem from far-field scattering or from strong near-field
of Ni–Al2O3 coatings was further improved by adding an ARC, and the scattering surrounding the metallic particles. The coupling of light

doi:10.1038/lsa.2014.42 Light: Science & Applications

 Solar energy
CF Guo et al
10

a b

1 mm 5 mm

|E|
c 4 Abs.,FEM Abs.,Analytic 8 d 1.2
Sca.,FEM Sca.,Analytic Normalized solar Normalized 400 °C black-
2 Ext.,FEM Ext.,Analytic Ex spectrum body radiation spectrum
6 1.0
0
4 4
Ex
0.8
Efficiency factor

2 kz

Reflectance
2
0
4 0 0.6
Ex
kz
2 Ex 0.4
0
4 Ex
kz 0.2
2

0 y 0.0
1 10
500 1000 1500 2000 2500 x
Wavelength (nm) Wavelength (mm)
z

Figure 12 (a, b) SEM images of as-synthesized and annealed Ni nanochain–Al2O3 composites. (c) 3D finite-element calculation along the chain direction of
absorption (magenta line), scattering (red line) and extinction (green line) efficiency factors vs. wavelengths for individual Ni nanochains with 1, 2, 6 and 10
nanospheres. (d) The reflectance of the Ni nanochain–Al2O3 cermet spectrally selective film. The normalized solar spectrum and 400 6C black body radiation are
also shown for reference. Figure reproduced with permission from Ref. 100, ß 2012 AIP. Abs, absorption; 3D, three-dimensional; Ext, extinction; FEM, finite-element
method; Sca, scattering; SEM, scanning electron microscopy.

into the SPP mode can significantly enhance light absorption in the We also briefly discussed metallic nanostructures in solar absorbers,
long wavelength region near the back contact. These structures can which are used for converting solar energy into heat and potentially for
significantly decrease the thickness of the active layer. The MIM struc- further converting this heat into electricity. Such solar absorbers
ture, a structure with a top metallic nanopattern and a thin dielectric require both high photo-thermal conversion efficiency and good dur-
on a metal substrate, is especially suitable for ultrathin photovoltaic ability at high temperature for CSP systems. We also proposed a novel
devices, for which light can be highly absorbed in an ,10 nm thick metallic filter nanostructure that may significantly simplify the process
active layer. Such ultrathin structures not only offer high efficiency of fabrication of solar absorbers and decrease the cost.
and low cost, but can also potentially be used as flexible solar cells.
ACKNOWLEDGMENTS
a b The work performed at the University of Houston was funded by the US
w Department of Energy under contract number DOE DE-FG02-13ER46917/DE-
SC0010831, and the work performed at the National Center for Nanoscience &
Technology of China was supported by the funds of NSFC (10974037), NBRPC
(2010CB934102), International S&T Cooperation Program (2010DFA51970) and
the ‘Strategic Priority Research Program’ of the Chinese Academy of Sciences
(Grant No. XDA09020300).

Figure 13 (a) A schematic illustration of a metallic nanofilter/absorbing layer/

metal substrate selective absorber. (b) Top view of the metallic nanofilter with a 1 Abbott D. Keeping the energy debate clean: how do we supply the world’s energy
mesh size of w. needs? Proc IEEE 2010; 98: 42–66.

Light: Science & Applications doi:10.1038/lsa.2014.42

 Solar energy
CF Guo et al
11

2 Weiss W, Mauthner F. International energy agency 2010, http://www.iea-shc.org 37 Ferry VE, Polman A, Atwater HA. Modeling light trapping in nanostructured solar cells.
3 Atwater HA, Polman A. Plasmonics for improved photovoltaic devices. Nat Mater ACS Nano 2011; 5: 10055–10064.
2010; 9: 205–213. 38 Ferry VE, Verschuuren MA, Li HB, Schropp RE, Atwater HA et al. Improved red-
4 Green MA, Emery K, Hishikawa Y, Warta W, Dunlop ED. Solar cell efficiency tables response in thin film a-Si:H solar cells with soft-imprinted plasmonic back
(version 39). Prog Photovoltaics 2012; 20: 12–20. reflectors. Appl Phys Lett 2009; 95: 183503.
5 Zhao J, Wang A, Green MA, Ferrazza F. 19.8% efficient ‘‘honeycomb’’ textured 39 Zhu J, Hsu CM, Yu Z, Fan S, Cui Y. Nanodome solar cells with efficient light
multicrystalline and 24.4% monocrystalline silicon solar cells. Appl Phys Lett management and self-cleaning. Nano Lett 2010; 10: 1979–1984.
1998; 73: 1991–1993. 40 Bowden N, Brittain S, Evans AG, Hutchinson JW, Whitesides GM. Spontaneous
6 Li T, Suo Z, Lacour SP, Wagner S. Compliant thin film patterns of stiff materials as formation of ordered structures in thin films of metals supported on an elastomeric
platforms for stretchable electronics. J Mater Res 2005; 20: 3274–3277. polymer. Nature 1998; 393: 146–149.
7 Lipomi DJ, Tee BC, Vosgueritchian M, Bao Z. Stretchable organic solar cells. Adv 41 Guo CF, Nayyar V, Zhang Z, Chen Y, Miao J et al. Path-guided wrinkling of nanoscale
Mater 2011; 23: 1771–1775. metal films. Adv Mater 2012; 24: 3010–3014.
8 Spinelli P, Ferry VE, van de Groep J, van Lare M, Verschuuren MA et al. Plasmonic light 42 Kim JB, Kim P, Pégard NC, Oh SJ, Kagan CR et al. Wrinkles and deep folds as photonic
trapping in thin-film Si solar cells. J Opt 2012; 14: 024002. structures in photovoltaics. Nature Photonics 2012; 6: 327–332.
9 Schaadt DM, Feng B, Yu ET. Enhanced semiconductor optical absorption via surface 43 Fabry C, Pérot A. Sur les franges des lames minces argentées et leur application à la
plasmon excitation in metal nanoparticles. Appl Phys Lett 2005; 86: 063106. mesure de petites épaisseurs d’air. Ann Chim Phys 1897; 12: 459–501.
10 Stuart HR, Hall DG. Island size effects in nanoparticle-enhanced photodetectors. Appl 44 Hadley LN, Dennison DM. Reflection and transmission interference filters (Part I.
Phys Lett 1998; 73: 3815–3817. Theory). J Opt Soc Am 1947; 37: 451–465.
11 Derkacs D, Lim SH, Matheu P, Mar W, Yu ET. Improved performance of amorphous 45 Hadley LN, Dennison DM. Reflection and transmission interference filters (Part II.
silicon solar cells via scattering from surface plasmon polaritons in nearby metallic Experimental, comparison with theory, results). J Opt Soc Am 1948; 38: 483–496.
nanoparticles. Appl Phys Lett 2006; 89: 093103. 46 Pendry JB, Holden AJ, Stewart WJ, Youngs I. Extremely low frequency plasmons in
12 Pillai S, Catchpole KR, Trupke T, Green MA. Surface plasmon enhanced silicon solar metallic mesostructures. Phys Rev Lett 1996; 76: 4773–4776.
cells. J Appl Phys 2007; 101: 093105. 47 Pendry JB, Holden AJ, Robbins DJ, Stewart WJ. Magnetism from conductors and
13 Nakayama K, Tanabe K, Atwater HA. Plasmonic nanoparticle enhanced light enhanced nonlinear phenomena. IEEE Trans Microwave Theory Tech 1999; 47:
absorption in GaAs solar cells. Appl Phys Lett 2008; 93: 121904. 2075–2084
14 Mokkapati S, Beck FJ, Polman A, Catchpole KR. Designing periodic arrays of metal 48 Smith DR, Padilla WJ, Vier DC, Nemat-Nasser SC, Schultz S. Composite medium with
nanoparticles for light-trapping applications in solar cells. Appl Phys Lett 2009; 95: simultaneously negative permeability and permittivity. Phys Rev Lett 2000; 84:
053115. 4184–4187.
15 Catchpole KR, Polman A. Design principles for particle plasmon enhanced solar cells. 49 Schurig D, Mock JJ, Justice BJ, Cummer SA, Pendry JB et al. Metamaterial
Appl Phy Lett 2008; 93: 191113. electromagnetic cloak at microwave frequencies. Science 2006; 314: 977–980.
16 Catchpole KR, Polman A. Plasmonic solar cells. Opt Express 2008; 16: 21793– 50 Liu X, Starr T, Starr AF, Padilla WJ. Infrared spatial and frequency selective
21800. metamaterial with near-unity absorbance. Phys Rev Lett 2010; 104: 207403.
17 Pillai S, Green MA. Plasmonics for photovoltaic applications. Sol Energ Mater Sol C 51 Pendry JB. Negative refraction makes a perfect lens. Phys Rev Lett 2000; 85: 3966–
Cells 2010; 94: 1481–1486. 3969.
18 Beck FJ, Polman A, Catchpole KR. Tunable light trapping for solar cells using localized 52 Padilla WJ, Basov DN, Smith DR. Negative refractive index metamaterials. Mater
surface plasmons. J Appl Phys 2009; 105: 114310. Today 2006; 9: 28–35.
19 Munday JN, Atwater HA. Large integrated absorption enhancement in plasmonic solar 53 Smith DR, Pendry JB, Wiltshire MC. Metamaterials and negative refractive index.
cells by combining metallic gratings and antireflection coatings. Nano Lett 2011; 11: Science 2004; 305: 788–792.
2195–2201. 54 Shalaev VM. Optical negative-index metamaterials. Nature Photonics 2007; 1: 41–48.
20 Du J, Qi J, Wang D, Tang Z. Facile synthesis of Au@TiO2 core–shell hollow spheres for 55 Soukoulis CM, Wegener M. Past achievements and future challenges in the
dye-sensitized solar cells with remarkably improved efficiency. Energy Environ Sci development of three-dimensional photonic metamaterials. Nature Photonics 2011;
2012; 5: 6914–6918 5: 523–530.
21 Rand BP, Peumans P, Forrest SR. Long-range absorption enhancement in organic 56 Hao J, Wang J, Liu X, Padilla WJ, Zhou L et al. High performance optical absorber
tandem thin-film solar cells containing silver nanoclusters. J Appl Phys 2004; 96: based on a plasmonic metamaterial. Appl Phys Lett 2010; 96: 251104.
7519–7526. 57 Zhang S, Fan W, Minhas BK, Frauenglass A, Malloy KJ et al. Midinfrared resonant
22 Kim SS, Na SI, Jo J, Kim DY, Nah YC. Plasmon enhanced performance of organic solar magnetic nanostructures exhibiting a negative permeability. Phys Rev Lett 2005; 94:
cells using electrodeposited Ag nanoparticles. Appl Phys Lett 2008; 93: 073307. 037402.
23 Wu JL, Chen FC, Hsiao YS, Chien FC, Chen P et al. Surface plasmonic effects of 58 Padilla WJ, Aronsson MT, Highstrete C, Lee M, Taylor AJ et al. Electrically resonant
metallic nanoparticles on the performance of polymer bulk heterojunction solar terahertz metamaterials: theoretical and experimental investigations. Phys Rev B
cells. ACS Nano 2011; 5: 959–967. 2007; 75: 041102(R).
24 Wang DH, Kim DY, Choi KW, Seo JH, Im SH et al. Enhancement of donor–acceptor 59 Gansel JK, Thiel M, Rill MS, Decker M, Bade K et al. Gold helix photonic metamaterial
polymer bulk heterojunction solar cell power conversion efficiencies by addition of Au as broadband circular polarizer. Science 2009; 325: 1513–1515.
nanoparticles. Angew Chem Int Ed 2011; 50: 5519–5523 60 Aydin K, Ferry VE, Briggs RM, Atwater HA. Broadband polarization-independent
25 Wang CC, Choy WC, Duan C, Fung DD, Sha WE et al. Optical and electrical effects of resonant light absorption using ultrathin plasmonic super absorbers. Nat Commun
gold nanoparticles in the active layer of polymer solar cells. J Mater Chem 2012; 22: 2011; 2: 517.
1206–1211. 61 Bayindir M, Aydin K, Ozbay E, Markoš P, Soukoulis CM. Transmission properties of
26 Konda RB, Mundle R, Mustafa H, Bamiduro O, Pradhan AK et al. Surface plasmon composite metamaterials in free space. Appl Phys Lett 2002; 81: 120–122.
excitation via Au nanoparticles in n-CdSe/p-Si heterojunction diodes. Appl Phys Lett 62 Greegor RB, Parazzoli CG, Li K, Tanielian MH. Origin of dissipative losses in negative
2007; 91: 191111. index of refraction materials. Appl Phys Lett 2003; 82: 2356–2358.
27 Hägglund C, Zäch M, Kasemo B. Enhanced charge carrier generation in dye sensitized 63 Garcı́a-Meca C, Ortuño R, Rodriguez-Fortuño FJ, Martı́ J, Martı́nez A. Double-negative
solar cells by nanoparticle plasmons. Appl Phys Lett 2008; 92: 013113. polarization-independent fishnet metamaterial in the visible spectrum. Opt Lett
28 Standridge SD, Schatz GC, Hupp JT. Distance dependence of plasmon-enhanced 2009; 34: 1603–1605.
photocurrent in dye-sensitized solar cells. J Am Chem Soc 2009; 131: 8407–8409. 64 Xiao SM, Chettiar UK, Kildishev AV, Drachev VP, Shalaev VM. Yellow-light negative-
29 Qi J, Dang X, Hammond PT, Belcher AM. Highly efficient plasmon-enhanced dye- index metamaterials. Opt Lett 2009; 34: 3478–3480.
sensitized solar cells through metal@oxide core–shell nanostructure. ACS Nano 65 Wang Y, Sun T, Paudel T, Zhang Y, Ren Z et al. Metamaterial-plasmonic absorber
2011; 5: 7108–7116. structure for high efficiency amorphous silicon solar cells. Nano Lett 2012; 12:
30 Brown MD, Suteewong T, Kumar RS, D’Innocenzo V, Petrozza A et al. Plasmonic dye- 4402445.
sensitized solar cells using core–shell metal–insulator nanoparticles. Nano Lett 66 Kats MA, Blanchard R, Genevet P, Capasso F. Nanometre optical coatings based on
2011; 11: 438–445. strong interference effects in highly absorbing media. Nat Mater 2013; 12: 20–24.
31 Choi H, Chen WT, Kamat PV. Know thy nano neighbor. Plasmonic versus electron 67 Sun T, Akinoglu EM, Guo CF, Paudel T, Gao J et al. Enhanced broad-band
charging effects of metal nanoparticles in dye-sensitized solar cells. ACS Nano extraordinary optical transmission through subwavelength perforated metallic films
2012; 6: 4418–4427. on strongly polarizable substrates. Appl Phys Lett 2013; 102: 101114.
32 Spinelli P, Polman A. Prospects of near-field plasmonic absorption enhancement in 68 Heavens OS. Optical Properties of Thin Solid Films. New York: Dover; 1965.
semiconductor materials using embedded Ag nanoparticles. Opt Express 2012; 20: 69 Guo CF, Sun T, Wang Y, Gao J, Liu Q et al. Conductive black silicon surface made by
A641–A654. silver nanonetwork assisted etching. Small 2013; 9: 2415–2419.
33 Green MA, Pillai S. Harnessing plasmonics for solar cells. Nature Photonics 2012; 6: 70 Guo CF, Sun T, Liu Q, Suo Z, Ren Z. Highly stretchable and transparent nanomesh
130–132. electrodes made by grain boundary lithography. Nat commun 2013; 5: 3121.
34 Ferry VE, Sweatlock LA, Pacifici D, Atwater HA. Plasmonic nanostructure design for 71 Wu H, Kong D, Ruan Z, Hsu PC, Wang S et al. A transparent electrode based on a metal
efficient light coupling into solar cells. Nano Lett 2008; 8: 4391–4397. nanotrough network. Nat Nanotech 2013; 8: 421–425.
35 Ferry VE, Munday JN, Atwater HA. Design considerations for plasmonic photovoltaics. 72 van de Groep J, Spinelli P, Polman A. Transparent conducting silver nanowire
Adv Mater 2010; 22: 4794–4808. networks. Nano Lett 2012; 12: 3138–3144.
36 Wang W, Wu S, Reinhardt K, Lu Y, Chen S. Broadband light absorption enhancement 73 Mauthner F, Weiss W. Solar Heat Worldwide: Solar Heating & Cooling Programme.
in thin-film silicon solar cells. Nano Lett 2010; 10: 2012–2018. Paris: International Energy Agency; 2013.

doi:10.1038/lsa.2014.42 Light: Science & Applications

 Solar energy
CF Guo et al
12

74 Kraemer D, Poudel B, Feng HP, Caylor JC, Yu B et al. High-performance flat-panel 91 Lampert CM, Washburn J. Microrstructure and optical properties of black chrome
solar thermoelectric generators with high thermal concentration. Nat Mater 2011; 10: before and after exposure to high temperatures. In: Proceedings of the Second
532–538. Annual Conference on Absorber Surfaces for Solar Receivers; 24–25 January 1979;
75 Kennedy CE. Review of mid- to high- temperature solar selective absorber materials. Boulder, CO, USA.
National Renewable Energy Laboratory: Golden, CO, USA, 2002. Report no. NREL/ 92 Boström T, Wäckelgård E, Westin G. Solution-chemical derived nickel–alumina
TP-520-31267 coatings for thermal solar absorbers. Sol Energy 2003; 74: 497–503.
76 Zhang QC. Optimizing analysis of W-AlN cermet solar absorbing coatings. J Phys D 93 Boström TK, Wäckelgård E, Westin G. Anti-reflection coatings for solution-chemically
Appl Phys 2001; 34: 3113–3120. derived nickel-alumina solar absorbers. Sol Energ Mat Sol C 2004; 84: 183–191.
77 Olson KD, Talghader JJ. Absorption to reflection transition in selective solar coatings. 94 Antonaia A, Castaldo A, Addonizio ML, Esposito S. Stability of W–Al2O3 cermet based
Opt Express 2012; 20: A554–A559. solar coating for receiver tube operating at high temperature. Sol Energ Mat Sol C
78 Tabor H. Selective radiation. I: wavelength discrimination. Bull Res Council Isr 1956; 2010; 94: 1604–1611.
5A: 119–134. 95 Cheng J, Wang C, Wang W, Du X, Liu Y et al. Improvement of thermal stability in the
79 Orel B, Spreizer H, Slemenik Perše L, Fir M, Šurca Vuk A et al. Silicone-based solar selective absorbing Mo–Al2O3 coating. Sol Energ Mat Sol C 2013; 109: 204–208.
thickness insensitive spectrally selective (TISS) paints as selective paint coatings 96 Zhang QC, Mills DR. Very low-emittance solar selective surfaces using new film
for coloured solar absorbers (Part I). Sol Energ Mat Sol C 2007; 91: 93–107. structures. J Appl Phys 1992; 72: 3013–3021.
80 Teixeira V, Sousa E, Costa MF, Nunes C, Rosa L et al. Spectrally selective composite 97 Zhang QC, Shen YG. High performance W–AlN cermet solar coatings designed by
coatings of Cr–Cr2O3 and Mo–Al2O3 for solar energy applications. Thin Solid Films modelling calculations and deposited by DC magnetron sputtering. Sol Energ Mat
2001; 392: 320–326. Sol C 2004; 81: 25–37.
81 Orel B, Orel ZC, Radoczy I. Thickness sensitive spectrally selective (TSSS) paint for 98 Zhang QC. Stainless-steel–AlN cermet selective surfaces deposited by direct current
solar collectors: optical properties, surface characterization and application magnetron sputtering technology. Sol Energ Mat Sol C 1998; 52: 95–106.
properties. Sol Energ Mater 1988; 18: 97–107. 99 Zhang QC, Mills DR. New cermet film structures with much improved selectivity for
82 Fan JC, Spura SA. Selective black absorbers using rf-sputtered Cr2O3/Cr cermet films. solar thermal applications. Appl Phys Lett 1992; 60: 545–547.
Appl Phys Lett 1977; 30: 511–513.
100 Wang X, Li H, Yu X, Shi X, Liu J. High-performance solution-processed plasmonic Ni
83 Craighead HG, Buhrman RA. Optical-properties of selectively absorbing Ni/Al2O3
nanochain–Al2O3 selective solar thermal absorbers. Appl Phys Lett 2012; 101:
composite films. Appl Phys Lett 1977; 31: 423–425.
203109.
84 Mcdonald GE. Spectral reflectance properties of black chrome for use as a solar
101 Byrne DM, Brouns AJ, Case FC, Tiberio RC, Whitehead BL et al. Infrared mesh filters
selective coating. Sol Energy 1975; 17: 119–122.
fabricated by electron-beam lithography. J Vac Sci Tech B Microelectron Nanometer
85 Narayanaswamy A, Chen G. Thermal emission control with one-dimensional
Struct 1985; 3: 268–271.
metallodielectric photonic crystals. Phys Rev B 2004; 70: 125101.
102 Jefimovs K, Laukkanen J, Vallius T, Pilvi T, Ritala M et al. Free-standing inductive grid
86 Barshilia HC, Selvakumar N, Vignesh G, Rajam KS, Biswas A. Optical properties and
filter for infrared radiation rejection. Microelectron Eng 2006; 83: 1339–1342.
thermal stability of pulsed-sputter-deposited AlxOy /Al/AlxOy multilayer absorber
103 Lee J, Lee P, Lee H, Lee D, Lee SS et al. Very long Ag nanowire synthesis and its
coatings. Sol Energ Mat Sol C 2009; 93: 315–323.
application in a highly transparent, conductive and flexible metal electrode touch
87 Nuru ZY, Arendse CJ, Khamlich S, Maaza M. Optimization of AlxOy /Pt/AlxOy multilayer
panel. Nanoscale 2012; 4: 6408–6414.
spectrally selective coatings for solar–thermal applications. Vacuum 2012; 86:
2129–2135.
88 Li XF, Chen YR, Miao J, Zhou P, Zheng YX et al. High solar absorption of a multilayered
thin film structure. Opt Express 2007; 15: 1907–1912. This work is licensed under a Creative Commons Attribution 3.0 Unported
89 Wu YW, Zheng WF, Lin LM, Qu Y, Lai FC. Colored solar selective absorbing coatings License. The images or other third party material in this article are included in
with metal Ti and dielectric AlN multilayer structure. Sol Energ Mat Sol C 2013; the article’s Creative Commons license, unless indicated otherwise in the credit
115: 145–150. line; if the material is not included under the Creative Commons license, users
90 Selvakumar N, Barshilia HC, Rajam KS, Biswas A. Structure, optical properties and will need to obtain permission from the license holder to reproduce the
thermal stability of pulsed sputter deposited high temperature HfOx/Mo/HfO2 solar material. To view a copy of this license, visit http://creativecommons.org/
selective absorbers. Sol Energ Mat Sol C 2010; 94: 1412–1420. licenses/by/3.0/

Light: Science & Applications doi:10.1038/lsa.2014.42