Solar Energy Materials & Solar Cells 144 (2016) 264272

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Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

A one-step solgel route derived AgCuO lm as a novel solar

selective absorber
Mengyao He, Yan Wang, Hongning Wang, Ruoyu Chen n
School of Chemistry and Chemical Engineering, Changzhou University, 1 Gehu Road, Changzhou, Jiangsu 213164, PR China

art ic l e i nf o a b s t r a c t

Article history: A novel one-step solgel method to fabricate spectrally selective solar absorber lm has been developed.
Received 27 April 2015 The selectively absorbing lm consists of Ag nano-particles grow in a semiconductor matrix of cupric
Received in revised form oxide (CuO). The inuence of the preparation conditions, i.e. the addition of diethanolamine (DEA) and
16 August 2015
tetraethylenepentamine (TEPA) and Ag /Cu2 molar ratios, on lm structure and optical properties
Accepted 17 September 2015
were studied. Texture properties (crystallinity, grain size, surface topography) were obtained by using
transmission electron microscopy (TEM), X-ray diffraction (XRD), eld emission scanning electron
Keywords: microscopy (FESEM) and atomic force microscopy (AFM). The results showed that the Ag nano-particles
AgCuO derived from TEPA had higher cystallization and better dispersibility, which were more conductive to the
Solgel
intrinsic absorption. Moreover, the heat treatment in the air did not oxidize the metallic Ag with the
Solar selective absorber lm
increased Ag /Cu2 molar ratios, but caused the longitudinal agglomeration among the nanoparticles of
Intrinsic absorption
Ag, thus led to a cone array structure on the lm surface and enhanced the intrinsic absorption. The
optical properties analysis of the fabricated lm revealed a normal solar absorptivity of 0.850 and low
thermal emissivity of 0.05. After adding an anti-reection layer, the absorptivity had been improved
to 0.917 while the thermal emittance remained unaltered. Hence AgCuO composite could be used as a
novel candidate material for solar selective absorber lms.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction high selectivity and durability and requires a cost-effective and

Nowadays the most widely used industrial solar selective
absorbers are metal particles in ceramic (cermet) structures which
are produced by electrochemical or vacuum deposition methods.
Some well-known examples include electroplated blackchrome
(CrCr2O3) and nickel-pigmented anodic Al2O3 (synthesized via
the electroplating/electrochemical method) as well as evaporated
titanium nitride lm (TiNOx) and nickel-nickel oxide (NiNiOx)
(synthesized via a vacuum deposition/sputtering method). The
electrochemical treatment methods are relatively simple and have
a low operating temperature, yet these methods utilize large
amounts of material and are not environmentally friendly [1,2].
Vacuum deposition methods are low in material consumption,
have good reproducibility and low levels of environmental pollu-
tion but they are, nonetheless, less cost-effective because they
require a large investment in rather complicated production
equipment with high operational cost and high energy intensity in
production [3,4]. Recent developments in the synthesis of selective
solar absorber highlight are the creation of a material which has
n
Corresponding author. Fax: 86 519 8633 0580.
E-mail address: cxdcry@163.com (R. Chen).
environmentally friendly synthesis process [5]. In this context, sol
gel techniques meet the criteria and they are very promising
techniques [6,7]. However, the application of these techniques to
produce solar selective absorber materials haven't been applied in
industry. Electrochemical or vacuum-based process is becoming
mainstream technology to develop the materials.
During the last decades, several kinds of solar selective absor-
bers have been successfully fabricated via solgel method, such as
copper oxide-based absorber, cobalt oxide-based absorber, black-
colored transition metal (Cu, Mn, Co, and Fe) oxides with spinel-
like structure and carbonsilica nanocomposite [8,9]. Never-
theless, to the best of our knowledge, the synthesis of cermet
coatings using solgel methods is relatively scarce. Efforts to fab-
ricate such ne structures were proved to be difcult. It is only
recently that solution-chemistry science is found to be an appro-
priate technique to synthesize this type of absorber. In 2003,
Bostrom and co-researchers [10] rst synthesized NiAl2O3 cermet
coatings by ejecting a precursor solution of nickel and aluminum
onto an aluminum substrate using a spin-coating technique. Pre-
cursor solutions of nickel and pure amorphous Al2O3 in different
proportions were mixed to control the nickel to alumina ratio in
the nal absorbing lms. During heat-treating process in an oxy-
gen free glass tube, the nickel ions had been reduced to nickel by

http://dx.doi.org/10.1016/j.solmat.2015.09.025
0927-0248/& 2015 Elsevier B.V. All rights reserved.
 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272 265

nitrogen and remained in the nal lm coating. Such prepared

absorbing layer with a nickel content of 65% could reach a solar
absorptance of 0.80. After that, further investigations [1113] by
Bostrom and co-researchers focused on improving the selectivity
and durability of the NiAl2O3 cermet and enhancing the perfor-
mance of the AR coatings. In summary, no other type of ceramic-
metal solar absorber has been prepared by solgel route so far.
In this work, we have developed a novel one-step solgel
method to fabricate spectrally selective solar absorber lms. Ag
CuO nanocomposite lm was rst synthetized for solar absorber
applications. The selectively absorbing lm consists of Ag nano-
particles grown in a semiconductor matrix of cupric oxide (CuO),
which has a similar structure with cermet coatings. CuO is selected
as the matrix because it has narrow band gap energies of 1.2 eV,
which has been actively investigated as a intrinsic absorber [14].
The inuence of the preparation conditions, i.e. the addition of
DEA and TEPA and Ag /Cu2 molar ratios, on lm structure and
optical properties were studied. A light absorption study for lms
within a wavelength range of 2502500 nm was conducted. One of
the most important advantages of this method is that the whole
preparation process including heat treatment can be carried out in
air atmosphere and thus the requirement for equipment can be
greatly reduced.
Fig. 1. Flow chart showing preparation of the AgCuO sol.

2. Experimental 2.4. Measurement techniques

2.1. Preparation of the sol
The synthesis of the sol was achieved using the following
synthesis route. In the condition of 20 C, silver nitrate was rstly
dissolved in absolute ethanol and then copper acetate was added
to the solution. The copper ion concentration in ethanol solution
was controlled in 0.2 mol/L. The molar ratio of silver nitrate to
copper acetate was adjusted to 0.08, 0.16, 0.32 and 0.64 in order to
t the optical property of the resulting lm. To this solution, tet-
raethylenepentamine (TEPA) or diethanolamine (DEA) used as a
complexing agent and a reducing agent with desired content was
slowly added under magnetic stirring. The resulting mixture was
kept stirring for 1 h until a deep blue dark sol generated. Finally
about 0.4 wt% of hydroxypropylcellulose (HPC) used as an organic
lmogen was added to the above sol to achieve the long-term
stability of the sol and obtain optimum viscosity for dip-coating
deposition. In some cases, SiO2 antireective coatings were sub-
sequently deposited by solgel following the procedure described
elsewhere [15]. Fig. 1 shows a ow charts of an optimized solgel
preparation process.
Solar absorptance (s) was calculated for the AM 1.5 solar
spectrum by using the hemispherical reectance spectrum from
250 to 2500 nm, which was recorded with a NIRvisUV Perkin-
Elmer Lambda 950 spectrophotometer. Thermal emittance (T)
was calculated using the hemispherical IR-reectance spectrum
and the black body spectrum at 25 C and the value at any tem-
perature can be calculated by setting the temperature value of T in
the emittance computational formula. IR spectra were recorded
from 2500 to 25,000 nm (i.e. 4000-400 cm  1) by means of a
Thermo Nicolet 6700 FTIR spectrophotometer. The phase struc-
tures within the lms were characterized by an X-ray dif-
fractometer (D/max 2500 PC) using monochromatized Cu-Ka
radiation. Coating sol was visualized using Transmission electron
microscopy (TEM, Jeol 2011, Japan). Field emission scanning elec-
tron microscopy (FESEM, SUPRA55, CarlZeiss) and atomic force
microscopy (AFM, Veeco, NanoMan VS) were employed for
detailed study of morphology and roughness of the lms. The LSPR
of Ag nanoparticles were measured using a UVvis spectrometer
(Shimadzu, UV-1700).

2.2. Cleaning procedure for the substrates 3. Result and discussion

The procedure for cleaning up the substrates was operated as
follows. The 1 mm-thick high-polished stainless steel foils (SS-304,
80  25 mm2) were successively treated ultrasonically in absolute
alcohol and acetone for 15 min. Then the substrates were com-
pletely cleaned up by deionized water. Well cleaned substrates
were dried off by blowing with N2.
2.3. Preparation of thin lms
AgCuO thin lms were deposited on well-cleaned SS-304
using the dip-coating technique from above sols with a pulling
speed of 8 cm/min at room temperature (  20 C). The coated
liquid lms were dried at 80 C for 20 min and annealed at 500 C
for 0.5 h using the heating rate of 1 C/min. All the samples just
undergo only a dipping/annealing cycle.
3.1. Effect of the DEA and TEPA on solar absorptance
The stabilizing action of the DEA or TEPA on the solgel system
is presented in two elds: one is its chelate forming ability with
the Cu2 , and another is its reducing ability with the Ag . In this
context, DEA and TEPA used as a complexing agent and a reducing
agent were rst studied in an effort to nd the better preparation
condition of the AgCuO lm for optical properties. Fixing the
ratio of Ag /Cu2 at 0.16, the DEA and TEPA with desired content
were respectively added and generated the transparent sol. Fig. 2
shows the TEM images of the coating sol. The selected area elec-
tron diffraction (SAED) patterns are indexed respectively. It bears
pointing out that the coating sols have not been heat-treated.
Cu2 must exist in the form of complex compound in solution.
As is seen, we can see that Ag nanoparticles are effectively
266 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272
Fig. 2. TEM images with the SAED pattern of the coating sol derived from DEA (a) and TEPA (b), respectively.
synthesized by chemical reduction route applied DEA and TEPA as
reducing agent. As shown in Fig. 2(b), the inset SAED pattern
revealed that the diffraction rings from inner to outer, with d-
spacings of 0.236, 0.2103, 0.142, and 0.122, could be indexed as
(111), (200), (220), and (311) reections, respectively, corre-
sponding to face-centered cubic silver. We can see Ag particles of
20  30 nm in size which has a spherical shape exist in the sol.
Fig. 2(a) shows the maximum particle-size of Ag nanoparticles is
only 20 nm. Moreover, there are rarely complete Ag nanoparticles
formed in the sol. The comparison of the diffraction rings suggests
that the Ag nanoparticles derived from TEPA has better poly-
crystalline as lattice planes clearly can be seen.
The crystallinity of the resultant Ag nanoparticles is directly
related to the reduction process of the reducting agent. Although
both DEA and TEPA have reducing nitrogen atoms, the reduction
mechanism of them are different. According to the complexing
reactions of Ag ions with triethanolamine (TEA) [16], the com-
plexing reaction of Ag ions with DEA (HN(CH2CH2OH)2, abbre-
viated as deaH2) can be assumed to follow a similar pathway,
expressed as:
AgNO3 [deaH3]OH-AgOH [deaH3]NO3
in excess of DEA:
AgOH 2[deaH3]OH-Ag(deaH2)2OH 2H2O
When DEA is added to a solution with AgNO3, precipitations
are observed, which can be explained by Reaction (1). After adding
enough DEA, the previously formed precipitate of AgOH or Ag2O is
completely dissolved under vigorous magnetic stirring, shown as
Reaction (2). The complex compound [Ag(deaH2)2]OH lowers the
redox potential of Ag, which causes Ag is easier to be deoxidized
to Ag0 [17].
However, as for the TEPA, it has several reducible nitrogen
atoms, which can be directly involved in the reduction process.
Due to the active group in the sol, such as eaq- (hydrated electron),
the Ag ions are easy to deoxidate. Ag atoms aggregate to clusters,
which can serve as nucleation cores [18]. Metallic Ag nanoparticles
disperse in the sol, forming Ag colloid. The corresponding reac-
tions are shown as below:
The XRD patterns of the scrapped lms derived from DEA and
TEPA after heated at 500 C are shown in Fig. 3. The peaks at 2
values of 38.06, 44.22, 64.36 and 77.32 can be assigned to the
diffraction lines produced by the (111), (200), (220) and (311)
planes of cubic Ag, respectively. Hybrid phase of AgO or Ag2O does
not appear although the heat treatment is carried out in an air
atmosphere. All the diffraction peaks can be perfectly indexed to
cubic Ag (JCPDS no. 04-0783) and monoclinic CuO (JCPDS no. 80-
1917), which indicate the lm is composed of pure AgCuO com-
posite. Subsequent to heat treatment, solvents are evaporated in
which only the metallic Ag and CuO remain in the nal lm
coating. The intrinsic absorption mechanism can be explained as
(1) below: c 1.24/Eg. Where c is the cut-off wavelength of the
absorber surface and Eg is the band gap. Only the wavelength less
than the c can cause the electron transition and achieve the
(2) photothermal conversion [19]. The uniform AgCuO particles
contain no impurities which can extend the c to long-wave
length, and then increase the absorption edge and rate. In addi-
tion, the relative intensity of the [111] diffraction line and peak
width (FWHM) of cubic Ag are presented as a table. As shown in
Table 1, the diffraction peaks of the powder samples become
weaker in intensity and wider when DEA is used for reducing
 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272
Fig. 3. XRD patterns of AgCuO powders prepared from a solution with different
reducing agent thermally treated at 500 C for 0.5 h and the standard JCPDS data.
Table 1
Relative intensity and peak width (FWHM) of the [111] diffraction line.
Chelating agent Relative intensity
TEPA 45,069
DEA 40,971
agent. The Ag nanoparticles have higher degree of crystallinity,
which is in good agreement with the TEM observations (Fig. 2).
The AgCuO lm samples derived from DEA and TEPA were
respectively subjected to FESEM analyses to gain the data of their
surface morphologies. In view of the atomic number of Ag is
higher, the bight white particles occurred on the surface of the
black particles are metallic silver. The boundary among the CuO
grains is not obvious due to the effect of Ag-doped. As shown in
Fig. 4(a) and (b), it causes the serious aggregation among the Ag
nanoparticles and results in the formation of many Ag clusters in
the size of 200300 nm when DEA is used as a reducing agent.
However, Fig. 4(c) and (d) shows the lm prepared from TEPA is
signicantly more compact and smooth in which Ag nanoparticles
are almost uniformly dispersed on the surface of CuO. The Ag
nanoparticles mostly exhibit a small size of 3040 nm and only a
fraction of them have merged into big ake. The discrepancies in
the morphology of AgCuO lm derived from DEA may be
attributed to the hard agglomeration came from poor crystallinity.
Due to the difculty in nucleation, Ag clusters tend to agglomerate
for further growth.
According to the FESEM images, we can nd that the particle
shapes of Ag and CuO are obviously different. The toplayer Ag are
large clusters, the underlayer CuO are akes, which boundary
among the CuO grains is not obvious. In order to identify each
component convincingly, We have made a new demonstration
experiment. The scrapped lms are subjected to TEM analyses to
gain the data of different particle shapes. As shown in Fig. 5, SAED
patterns of the ake suggests that the inter planar spacing of the
fringes perpendicular to the wire axis is 0.273 nm, corresponding
267
to the (110) planes of monoclinic CuO. The area of black grains are
indexed to be cubic silver. The result further examines our pre-
vious conclusion.
In order to check the quality of AgCuO composite as selective
absorbers, reectance spectra in the range 2502500 nm were
measured and solar absorptance was calculated for each case.
Fig. 6 displays that all the lms can reach a solar absorptance of
0.80, which can be compared to the NiAl2O3 cermet coatings [10].
Meanwhile, absorbing lm made from TEPA has better perfor-
mance since lower reection in UV and NIR spectra contributes to
its higher absorption ( 0.830). Undersized Ag nanoparticles
with poor crystallization can not play its intrinsic absorption well
in UVvis region. On the other hand, the Ag nanoparticles pre-
pared from TEPA have better dispersibility, thus lead to larger
solar-absorbing surface area. It can thus be concluded that TEPA
used as a chelating agent and a reducing agent is more suitable for
obtaining a good absorber layer.
3.2. Effect of Ag /Cu2 on solar absorptance
Secondly, various AgCuO lm samples prepared from different
Ag /Cu2 molar ratios were characterized to determine the
optimal composition for optical properties. Selecting TEPA as a
chelating agent, the ratio of Ag /Cu2 varies as 0.08, 0.16, 0.32
and 0.64, and the absorbing lm was prepared respectively. Var-
iations of XRD patterns for AgCuO lm samples with different
Ag /Cu2 molar ratios are shown in Fig. 7. As is seen, as the Ag /
Cu2 ratio increases, the diffraction peak intensity of cubic Ag on
[111], [200], [220] and [311] planes enhances correspondingly
while the intensity of monoclinic CuO gradually decreases. When
Ag /Cu2 0.64, the diffraction peaks of CuO on [002] and [202]
FWHM plane almost disappear. It's worth mentioning that the lm still
maintains its pure structure of AgCuO composite effectively.
0.273
0.278
There are no impurity phase forms with the increasing mole ratio
of Ag /Cu2 . The values of crystalline size estimated from the
halfwidth via the Scherrer formula according to the [111] and
[002] reection planes of Ag and CuO are presented as a table. As
shown in Table 2, the grain sizes of Ag is increased from 29.2 nm to
38.9 nm while CuO is increased from 58.3 nm to 66.2 nm. when
the sol transformed into gel, the Ag nanoparticles were uniformly
xed in the three-dimensional network. In heat-treatment, the
structure of gel network become more and more dense, the
migration of Ag ions gets serious obstacle, therefore, the grain size
of the resultant Ag nanoparticles have almost no change compared
with the Ag nanoparticles in the sol. In addition, the diffraction
peak of Ag on [111] plane shifts to small angle, which indicate the
lattice parameter of Ag increases according to the Bragg equation.
This change may be caused by the reunion of Ag nanoparticles.
FESEM photographs of the AgCuO lm samples prepared from
different Ag /Cu2 molar ratios are exhibited in Fig. 8. The results
show that the existence of Ag nanoparticles on the lm surface has
obviously changed. As shown in Fig. 8(a) and (b), the lm surface is
covered by Ag nanoparticles of about 30 nm when Ag /
Cu2 0.08, which keeps the overlook of the lm uniform and
dense. With the molar ratio of Ag /Cu2 increasing from 0.16 to
0.64, the evenly dispersed Ag nanoparticles grades into the state of
intercoagulation. Fig. 8(c)(h) displays that the formation of Ag
large nanocrystallines continues to grow on the surface, which
lead to the underlayer CuO gradually exposed. The Ag nano-
clusters exhibit longitudinal growth and thus higher void space
between the underlayer CuO and the toplayer Ag-clusters can be
formed. Hence, the effective surface area of the absorbing lm is
increased.
Meanwhile, the 3D AFM images of the above lms are shown in
Fig. 9. For the lm prepared by Ag /Cu2 0.08 and 0.16, the
surfaces are more dense and smooth and the arithmetic average
268 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272
Fig. 4. The FESEM images of the AgCuO lm samples prepared by DEA (a, b) and TEPA (c, d), respectively.
Fig. 5. TEM images of scrapped lms (with SAED patterns).
height deviation (Ra) value are just 6.5 nm and 12.2 nm (Fig. 9
(a) and (b)). Our statistical analysis shows that the surface
roughness of the lms increased with the Ag /Cu2 mole ratios,
that is, because the Ag nano-clusters, growing in the matrix of CuO
in which the lm presents the structure featured of a peak and
valley structure (Fig. 9(c) and (d)). In regard to surface roughness
of the lm derived from Ag /Cu2 0.32 and 0.64, Ra values are
found to be 21.0 nm and 26.7 nm respectively. Roughness is a key
factor, which decreases the front surface reection, and the
absorption might increase with the increase of roughness. When
light spectra encounter the absorber surface, some of them enter
into the lm and some of them are reected. When a peak and
valley structure absorber is used, light can be effectively trapped in
the inner structure by mutireection [20] on the surface of indi-
vidual peak. As a consequence, the intrinsic absorption of AgCuO
can be enhanced.
In Fig. 10 we have recorded reectance spectra and the corre-
sponding values of both absorptance and emittance of four sam-
ples of AgCuO based absorber. As is seen, all the lms can reach a
normal solar absorptance of 0.80, of which lm prepared by Ag /
Cu2 0.32 has the best performance ( 0.848). With the Ag /
Cu2 molar ratio increased from 0.08 to 0.32, the reectance in
UVvis range of the lms continually decreases, meanwhile, the
absorption edge in the NIR range (8001200 nm) shifts toward
longer wavelengths. Moreover, lowest reection in 14002500 nm
is another reason that leads to a high absorption of the lm pre-
pared by Ag /Cu2 0.32. However, under the consideration of
optical properties and experimental cost, the solution with molar
ratio Ag /Cu2 0.64 is not suitable for obtaining a good
absorber layer.
 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272 269

The existence of numerous spin-allowed electron transitions

between partially lled d-orbitals contributes to the high absorp-
tion levels of Ag and CuO across the whole solar radiation spec-
trum. The optical properties of the samples are optimized with the
molar ratio of Ag/Cu increase from 0.08 to 0.32, this is mainly
displays in two aspects, one is the reectance in UVvis decreases,
and the other is the absorption edge in the NIR shifts toward a
longer wavelengths. We suppose there are two reasons for this
kind of optimization. As shown in FESEM images, the evenly dis-
persed Ag nanoparticles grades into the state of intercoagulation
with the increasing molar ratio. The Ag nano-clusters exhibit
longitudinal growth and thus higher void space between the
underlayer CuO and the toplayer Ag-clusters can be formed. Due to
the interfacial and bulk effect, the AgCuO composite lm can
possess high optical absorption capacity, which is the main reason
that lower the reectance of the lm in UVvis range. Moreover, as
shown in AFM, a peak and valley structure is formed over the lm
surface. The surface of microstructure may has an optical trap for
Fig. 6. Reectance spectra of AgCuO absorbing lms prepared from DEA near infrared, which causes the absorption edge in the NIR shifts
and TEPA. toward a longer wavelengths.
However, as shown in Fig. 8(g) and (h), the growth of Ag nano-
clusters is near saturation under the molar ratio of Ag /
Cu2 0.64. Many Ag nanocrystals in size of  300 nm which
compared with the wavelength of incident ray have been gener-
ated. The absorptance of the tandem absorber was calculated from
the UVvisNIR reectance proles using the law of conservation
of energy: A R T 1, where, A, R and T are absorptance, reec-
tance and transmittance, respectively. Here, the SS substrates we
have used in experiment were usually standardized, which the
surface reecting characters were xed. In other words, the
emittance values of SS-304 substrate are found to be 0.045, which
the error is limited in 0.003. The substrate reection of all the lm
samples are nearly the same, which will not inuence the reec-
tion capability for lm. The transmittance is zero because the Ag
CuO absorber was deposited on SS substrate. Since the grain size
as well as the morphology of CuO almost unchanged, the reection
of the absorber is mainly affected by the morphology of Ag
nanocrystals when light spectra encounter the absorber surface.
Ag nanocrystals in size of  300 nm may lead to an increase in
reection of the incident light wave at  600 nm, which is not
Fig. 7. Variations of XRD patterns for AgCuO lm samples with different Ag / conducive to absorption.
Cu2 molar ratios. In addition, Ag nanoparticles, as a typical plasmonic material,
can exhibit more remarkable localized surface plasmon (LSPR)
absorption in the solar spectrum. In simple terms, LSPR is made up
Table 2 of collective oscillations of free electrons in metal NPs driven by
The values of crystalline size estimated from the half-width via the Scherrer for- the electromagnetic eld of incident light. The LSPR of nano-
mula according to the [111] and [002] reection planes of Ag and CuO. particles can be readily measured using a UVvis spectrometer,
and it appears as an absorption band in the UVvis spectrum. In
Ag / Ag [111] 2 Ag [111] Ag grain CuO CuO [002] CuO grain
Cu2 FWHM size (nm) [002] 2 FWHM size (nm) this case, we have deposited AgCuO composite lms on quartz
glass under the molar ratio of Ag /Cu2 0.32, so that the LSPR
0.08 38.059 0.273 29.2 35.460 0.309 58.3 absorption feature can be seen. LSPR spectrum for the lm sample
0.16 38.058 0.219 36.5 35.460 0.298 60.5 is shown in Fig. 11. As shown in Fig. 11, the wavelength of max-
0.32 38.058 0.215 37.2 35.460 0.285 63.3
0.64 38.041 0.216 38.9 35.460 0.272 66.2
imum LSPR absorption (max) is 342 nm. The intensity and wave-
length of LSPR absorption depended on the size, morphology, and
aspect ratio of the Ag nanoparticles. Lack of time forbids any fur-
In this context, we have created an absorberreector tandem ther discussion at the point. However, there is no doubt that the
concept (AgCuO lm-SS substrate). It is very useful where a LSPR absorption of Ag partially contributes to the high absorption
levels of the whole AgCuO lm across the solar radiation
highly visible light absorbing coating showing minimum absorp-
spectrum.
tion in the thermal IR region ( 42.5 m) is being applied on the
IR reecting metal substrates. Transparency of the coated surface
3.3. Anti-refection treatment
toward thermal radiation makes it possible to determine the
emittance value of the selective absorber system from the It is worth noting that all the AgCuO lm samples we have
reecting metal substrate which is basically very low [21]. From made show a reectance maximum in the Vis range of around
Fig. 10, we can see the emittance value stays constant at 0.04, 500 nm, which is an undesired phenomenon, since it reduces the
which closes to the SS-304 substrate (0.055). solar absorptance value. Unlike the insulators used in the efcient
270 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272

Fig. 8. The FESEM surface images of the AgCuO lms prepared from the Ag /Cu2 0.08 (a, b); Ag /Cu2 0.16 (c, d); Ag /Cu2 0.32 (e, f); Ag /Cu2 0.64 (g, h).

cermets such as Al2O3, MgO, SiO2, etc, having a refractive index low value for this AgCuO/SS system to be used as selective
less than 2 in the visible region [22], the refractive index of CuO absorber. In order to decreases the reectance in the Vis range and
summed up to 2.63. The higher refractive index of the whole lm hence to improve the absorptance, a SiO2 antireective coating is
go against low reection. Solar absorptance around 0.85 is still too subsequently deposited onto the AgCuO layer. For a material to
 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272
Fig. 9. AFM topography of the AgCuO lms prepared using the four Ag /Cu2 mole ratios: (a) 0.08, (b) 0.16, (c) 0.32, (d) 0.64.
Fig. 10. Reectance spectra of AgCuO lms prepared from a solution with dif-
ferent Ag /Cu2 ratios.
be used as antireective coating for a certain surface it needs to
have a refractive index between the value of the material under-
neath and the value of the air (n 1). For the case of AgCuO
composite, no data have been found in the literature about its
refractive index. However, since CuO has refractive index around
2.63, we can assume such value for our compound. Therefore, as
SiO2 refractive index is 1.5, it should be a good choice as antire-
ective material for our absorber layer. In Fig. 12, the reectance
spectra corresponding to samples deposited from a solution with
metallic ratio Ag /Cu2 0.32 before and after depositing the
SiO2 coating are displayed. As is seen, antireecting effect makes
the absorption edge shift towards longer wavelengths and reec-
tance maximum in the Vis range is dramatically decreased. An
improvement of up to 13% units in solar absorptance was obtained
while the thermal emittance value remained fairly constant. The
absorptance value increased from 0.850 to 0.917 after adding the
AR layer while the emittance value stays constant at 0.05.
271
Fig. 11. LSPR spectrums for AgCuO lm deposited on quartz glass under the molar
ratio of Ag /Cu2 0.32.
4. Conclusion
In this study, AgCuO absorbing lm without the impurity
phase was successfully synthesized using a one-step solgel dip-
coating method. The process is simple, utilizes readily available
chemicals and does not demand sophisticated equipment. TEM
and XRD analysis results indicated that the Ag nano-particles were
shaped in the sol preparation process and nally remained in the
lm. Furthermore, Ag nano-particles derived from TEPA had
higher cystallization and better dispersibility. Morphology analysis
displayed that the longitudinal growth of the Ag nano-particles
formed a cone structure on the lm surface with the increasing
molar ratio of Ag /Cu2 , which is favorable for light trapping and
surface reection reduction. The lm reached a promising solar
absorptance of 0.92 and a normal thermal emittance of 0.05, even
without optimizing the anti-reection layer. Hence, AgCuO lm
can be a potential candidate for spectrally selective absorbers in
solarthermal energy conversion systems.
272 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272
Fig. 12. Reectance spectra for AgCuO lm before and after an anti-reection
treatment. The corresponding solar absorptance values and emittance values are
also recorded.
Acknowledgments
The authors acknowledge the nancial support of the Project
supported by National Natural Science Foundation of China (Grant
no. 21101017/B0107; no. 21571024), Industry and Research Per-
spective in Jiangsu Province (Grant no. BY2015027-01) and the
Innovation Project of Postgraduates in Jiangsu Province
(CXZZ13_0728).
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