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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.
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
2.1. Preparation of the sol Solar absorptance (s) was calculated for the AM 1.5 solar
spectrum by using the hemispherical reectance spectrum from
The synthesis of the sol was achieved using the following 250 to 2500 nm, which was recorded with a NIRvisUV Perkin-
synthesis route. In the condition of 20 C, silver nitrate was rstly Elmer Lambda 950 spectrophotometer. Thermal emittance (T)
dissolved in absolute ethanol and then copper acetate was added was calculated using the hemispherical IR-reectance spectrum
to the solution. The copper ion concentration in ethanol solution and the black body spectrum at 25 C and the value at any tem-
was controlled in 0.2 mol/L. The molar ratio of silver nitrate to perature can be calculated by setting the temperature value of T in
copper acetate was adjusted to 0.08, 0.16, 0.32 and 0.64 in order to the emittance computational formula. IR spectra were recorded
t the optical property of the resulting lm. To this solution, tet- from 2500 to 25,000 nm (i.e. 4000-400 cm 1) by means of a
raethylenepentamine (TEPA) or diethanolamine (DEA) used as a Thermo Nicolet 6700 FTIR spectrophotometer. The phase struc-
complexing agent and a reducing agent with desired content was tures within the lms were characterized by an X-ray dif-
slowly added under magnetic stirring. The resulting mixture was fractometer (D/max 2500 PC) using monochromatized Cu-Ka
kept stirring for 1 h until a deep blue dark sol generated. Finally radiation. Coating sol was visualized using Transmission electron
about 0.4 wt% of hydroxypropylcellulose (HPC) used as an organic microscopy (TEM, Jeol 2011, Japan). Field emission scanning elec-
lmogen was added to the above sol to achieve the long-term tron microscopy (FESEM, SUPRA55, CarlZeiss) and atomic force
stability of the sol and obtain optimum viscosity for dip-coating microscopy (AFM, Veeco, NanoMan VS) were employed for
deposition. In some cases, SiO2 antireective coatings were sub- detailed study of morphology and roughness of the lms. The LSPR
sequently deposited by solgel following the procedure described of Ag nanoparticles were measured using a UVvis spectrometer
elsewhere [15]. Fig. 1 shows a ow charts of an optimized solgel (Shimadzu, UV-1700).
preparation process.
The procedure for cleaning up the substrates was operated as 3.1. Effect of the DEA and TEPA on solar absorptance
follows. The 1 mm-thick high-polished stainless steel foils (SS-304,
80 25 mm2) were successively treated ultrasonically in absolute The stabilizing action of the DEA or TEPA on the solgel system
alcohol and acetone for 15 min. Then the substrates were com- is presented in two elds: one is its chelate forming ability with
pletely cleaned up by deionized water. Well cleaned substrates the Cu2 , and another is its reducing ability with the Ag . In this
were dried off by blowing with N2. context, DEA and TEPA used as a complexing agent and a reducing
agent were rst studied in an effort to nd the better preparation
2.3. Preparation of thin lms condition of the AgCuO lm for optical properties. Fixing the
ratio of Ag /Cu2 at 0.16, the DEA and TEPA with desired content
AgCuO thin lms were deposited on well-cleaned SS-304 were respectively added and generated the transparent sol. Fig. 2
using the dip-coating technique from above sols with a pulling shows the TEM images of the coating sol. The selected area elec-
speed of 8 cm/min at room temperature ( 20 C). The coated tron diffraction (SAED) patterns are indexed respectively. It bears
liquid lms were dried at 80 C for 20 min and annealed at 500 C pointing out that the coating sols have not been heat-treated.
for 0.5 h using the heating rate of 1 C/min. All the samples just Cu2 must exist in the form of complex compound in solution.
undergo only a dipping/annealing cycle. 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 redox potential of Ag, which causes Ag is easier to be deoxidized
reducing agent. As shown in Fig. 2(b), the inset SAED pattern to Ag0 [17].
revealed that the diffraction rings from inner to outer, with d- However, as for the TEPA, it has several reducible nitrogen
spacings of 0.236, 0.2103, 0.142, and 0.122, could be indexed as atoms, which can be directly involved in the reduction process.
(111), (200), (220), and (311) reections, respectively, corre- Due to the active group in the sol, such as eaq- (hydrated electron),
sponding to face-centered cubic silver. We can see Ag particles of the Ag ions are easy to deoxidate. Ag atoms aggregate to clusters,
20 30 nm in size which has a spherical shape exist in the sol. which can serve as nucleation cores [18]. Metallic Ag nanoparticles
Fig. 2(a) shows the maximum particle-size of Ag nanoparticles is disperse in the sol, forming Ag colloid. The corresponding reac-
only 20 nm. Moreover, there are rarely complete Ag nanoparticles tions are shown as below:
formed in the sol. The comparison of the diffraction rings suggests The XRD patterns of the scrapped lms derived from DEA and
that the Ag nanoparticles derived from TEPA has better poly- TEPA after heated at 500 C are shown in Fig. 3. The peaks at 2
crystalline as lattice planes clearly can be seen. values of 38.06, 44.22, 64.36 and 77.32 can be assigned to the
The crystallinity of the resultant Ag nanoparticles is directly diffraction lines produced by the (111), (200), (220) and (311)
related to the reduction process of the reducting agent. Although planes of cubic Ag, respectively. Hybrid phase of AgO or Ag2O does
both DEA and TEPA have reducing nitrogen atoms, the reduction not appear although the heat treatment is carried out in an air
mechanism of them are different. According to the complexing atmosphere. All the diffraction peaks can be perfectly indexed to
reactions of Ag ions with triethanolamine (TEA) [16], the com- cubic Ag (JCPDS no. 04-0783) and monoclinic CuO (JCPDS no. 80-
plexing reaction of Ag ions with DEA (HN(CH2CH2OH)2, abbre- 1917), which indicate the lm is composed of pure AgCuO com-
viated as deaH2) can be assumed to follow a similar pathway, posite. Subsequent to heat treatment, solvents are evaporated in
expressed as: which only the metallic Ag and CuO remain in the nal lm
coating. The intrinsic absorption mechanism can be explained as
AgNO3 [deaH3]OH-AgOH [deaH3]NO3 (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
in excess of DEA:
than the c can cause the electron transition and achieve the
AgOH 2[deaH3]OH-Ag(deaH2)2OH 2H2O (2) photothermal conversion [19]. The uniform AgCuO particles
contain no impurities which can extend the c to long-wave
When DEA is added to a solution with AgNO3, precipitations length, and then increase the absorption edge and rate. In addi-
are observed, which can be explained by Reaction (1). After adding tion, the relative intensity of the [111] diffraction line and peak
enough DEA, the previously formed precipitate of AgOH or Ag2O is width (FWHM) of cubic Ag are presented as a table. As shown in
completely dissolved under vigorous magnetic stirring, shown as Table 1, the diffraction peaks of the powder samples become
Reaction (2). The complex compound [Ag(deaH2)2]OH lowers the weaker in intensity and wider when DEA is used for reducing
M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272 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.
Fig. 4. The FESEM images of the AgCuO lm samples prepared by DEA (a, b) and TEPA (c, d), respectively.
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 271
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. 11. LSPR spectrums for AgCuO lm deposited on quartz glass under the molar
Fig. 10. Reectance spectra of AgCuO lms prepared from a solution with dif- ratio of Ag /Cu2 0.32.
ferent Ag /Cu2 ratios.
4. Conclusion
be used as antireective coating for a certain surface it needs to
have a refractive index between the value of the material under- In this study, AgCuO absorbing lm without the impurity
neath and the value of the air (n 1). For the case of AgCuO phase was successfully synthesized using a one-step solgel dip-
composite, no data have been found in the literature about its coating method. The process is simple, utilizes readily available
refractive index. However, since CuO has refractive index around chemicals and does not demand sophisticated equipment. TEM
2.63, we can assume such value for our compound. Therefore, as and XRD analysis results indicated that the Ag nano-particles were
SiO2 refractive index is 1.5, it should be a good choice as antire- shaped in the sol preparation process and nally remained in the
ective material for our absorber layer. In Fig. 12, the reectance lm. Furthermore, Ag nano-particles derived from TEPA had
spectra corresponding to samples deposited from a solution with higher cystallization and better dispersibility. Morphology analysis
metallic ratio Ag /Cu2 0.32 before and after depositing the displayed that the longitudinal growth of the Ag nano-particles
SiO2 coating are displayed. As is seen, antireecting effect makes formed a cone structure on the lm surface with the increasing
the absorption edge shift towards longer wavelengths and reec- molar ratio of Ag /Cu2 , which is favorable for light trapping and
tance maximum in the Vis range is dramatically decreased. An surface reection reduction. The lm reached a promising solar
improvement of up to 13% units in solar absorptance was obtained absorptance of 0.92 and a normal thermal emittance of 0.05, even
while the thermal emittance value remained fairly constant. The without optimizing the anti-reection layer. Hence, AgCuO lm
absorptance value increased from 0.850 to 0.917 after adding the can be a potential candidate for spectrally selective absorbers in
AR layer while the emittance value stays constant at 0.05. solarthermal energy conversion systems.
272 M. He et al. / Solar Energy Materials & Solar Cells 144 (2016) 264272