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TiAlN/TiAlON/Si3N4 Tandem Absorber for High

Temperature Solar Selective Applications

ARTICLE in APPLIED PHYSICS LETTERS · NOVEMBER 2006

Impact Factor: 3.3 · DOI: 10.1063/1.2387897

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 APPLIED PHYSICS LETTERS 89, 191909 共2006兲

TiAlN / TiAlON / Si3N4 tandem absorber for high temperature solar selective
applications
Harish C. Barshilia,a兲 N. Selvakumar, and K. S. Rajam
Surface Engineering Division, National Aerospace Laboratories, Bangalore 560 017, India
D. V. Sridhara Rao and K. Muraleedharan
Electron Microscopy Group, Defence Metallurgical Research Laboratory, Hyderabad 500 058, India
A. Biswas
Spectroscopy Division, Bhabha Atomic Research Center, Mumbai 400 085, India
共Received 10 August 2006; accepted 26 September 2006; published online 8 November 2006兲
A tandem absorber of TiAlN / TiAlON / Si3N4 is prepared using a magnetron sputtering process. The
graded composition of the individual component layers of the tandem absorber produces a film with
a refractive index increasing from the surface to the substrate, which exhibits a high absorptance
共0.95兲 and a low emittance 共0.07兲. The tandem absorber is stable in air up to 600 ° C
for 2 h, indicating its importance for high temperature solar selective applications. The thermal
stability of the tandem absorber is attributed to high oxidation resistance and microstructural
stability of the component materials at higher temperatures. © 2006 American Institute of Physics.
关DOI: 10.1063/1.2387897兴

Spectrally selective coatings used in solar collectors are
known to enhance the efficiency of photothermal conversion.
The main requirements for the solar selective absorbers for
high temperature applications are high absorptance 共␣兲 in the
wavelength range of 0.3– 2.5 ␮m and low emittance 共␧兲 at
higher operating temperatures. The ideal characteristics of a
photothermal converter can be approximated by an absorber-
reflector tandem, in which the reflector is coated with a layer
which is highly absorbing over the visible region and is
transparent in the infrared 共IR兲 region. Generally, the tandem
absorbers degrade at higher operating temperatures because
of unstable microstructure, which causes a decrease in the
solar selectivity 共␣ / ␧兲. A large number of high temperature
solar selective coatings have been studied such as M – Al2O3
共M = Pt, Ni, Mo, Cu兲 cermets, M – AlN 共M = W, Mo, stainless
steel兲 cermets, etc.1–3 These cermet coatings have been found
to be stable in air up to 400– 600 ° C. For high temperature
applications, low ␧ is an important parameter, because the
thermal radiative losses of the absorbers increase proportion-
ally as T4.4
In recent years, TiAlN and TiAlON have been developed
for various applications such as electronics devices, diffusion
barriers, and hard coatings.5–8 Both TiAlN and TiAlON ex-
hibit superior mechanical, electrical, and oxidation properties
at higher temperatures 共up to 800 ° C兲. The optical properties
of TiAlN and TiAlON have rarely been studied.5,8 The opti-
cal properties of “Ti” based nitride coatings can be tailored
by controlling the stoichiometry, which affects the density of
free electrons in the d band.5,9 Incorporation of Al and O in
TiN changes the bonding structure 共e.g., metallic to cova-
lent兲. This results in variations in the electrical resistivity and
the optical properties of TiAlN and TiAlON. Therefore,
TiAlN / TiAlON coating deposited on a metal substrate is
expected to have graded refractive index, resulting in high
absorptance and low emittance. The absorptance of the
a兲
Author to whom correspondence should be addressed; electronic mail:
harish@css.nal.res.in
TiAlN / TiAlON absorber can be further improved by em-
ploying a suitable antireflection coating 共e.g., Si3N4兲.
In this letter, we describe a solar selective coating of
TiAlN / TiAlON / Si3N4 deposited using a magnetron sputter-
ing process. The first absorber layer 共i.e., TiAlN兲 consists of
a high metal volume fraction as compared to the second ab-
sorber layer 共i.e., TiAlON兲. The third layer 共Si3N4兲, a dielec-
tric in nature, acts as an antireflection coating. The composi-
tions and the thicknesses of the individual component layers
have been optimized to achieve a tandem absorber with
graded refractive index profile. This tandem absorber exhib-
its a high solar selectivity 共⬃14兲 and is thermally stable in
air.
The tandem absorbers were deposited at room tempera-
ture on metal and nonmetal substrates using a reactive direct
current magnetron sputtering system. TiAlN, TiAlON, and
Si3N4 layers were deposited using reactive sputtering of TiAl
共50:50兲 and Si targets in Ar+ N2, Ar+ N2 + O2, and Ar+ N2
plasmas, respectively. The process parameters such as power
density, N2 and O2 flow rates, and layer thicknesses were
optimized to achieve high solar selectivity.10 The chemical
bonding of TiAlN, TiAlON, and Si3N4 was confirmed using
x-ray photoelectron spectroscopy.
Figure 1共a兲 shows a three-dimensional atomic force mi-
croscopy image of the TiAlN / TiAlON / Si3N4 tandem ab-
sorber deposited on a copper substrate. The tandem absorber
exhibited a rms roughness of 12.5 nm. The bright field cross-
sectional transmission electron microscopy 共XTEM兲 micro-
graph of the tandem absorber deposited on a Si substrate is
shown in Fig. 1共b兲. From the XTEM micrograph, the layer
thicknesses of TiAlN, TiAlON, and Si3N4 were found to be
approximately 64, 24, and 34 nm, respectively. The dark
field XTEM images at higher magnification clearly indicated
that TiAlN and TiAlON were nanocrystalline 共crystallite
size= 3 – 5 nm兲, whereas Si3N4 was amorphous. These results
were supported by selected area diffraction 共SAD兲. For the
diffraction measurements, the SAD aperture was selected in
such a way as to cover all the three layers. The SAD pattern

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191909-2 Barshilia et al.
FIG. 1. 共Color online兲 AFM image of the surface of TiAlN / TiAlON / Si3N4 tandem absorber. 共b兲 XTEM micrograph of the tandem absorber, showing
individual layers of TiAlN, TiAlON, and Si3N4. 共c兲 Corresponding SAD pattern, indicating nanocrystalline nature of TiAlN and TiAlON.
关Fig. 1共c兲兴 showed a spotty ring pattern, indicating a nano-
crystalline nature and absence of texture. The d values cal-
culated from diffraction rings 1, 3, 6, 7, and 8 closely
matched with 共111兲, 共200兲, 共220兲, 共311兲, and 共400兲 planes,
respectively, of B1 cubic TiN; however, diffraction rings 2,
4, and 5 could not be matched. The origin of these diffraction
spots may be attributed to the formation of Ti3AlN and
Ti3AlON metastable phases. Detailed investigations using
high-resolution TEM confirmed the nanocrystalline nature of
TiAlN and TiAlON.11
The electrical resistivities of TiAlN and TiAlON layers
deposited on glass substrates were of the orders of 0.02–0.04
and 10– 20 ⍀ cm, respectively. Si3N4 is a well-known di-
electric with very high resistivity 共1010 – 1014 ⍀ cm兲. Rela-
tively high resistivity of TiAlON indicates its more dielectric
and less metallic character, suggesting a low metal volume
fraction for TiAlON as compared to TiAlN. The optimized
Cu/ TiAlN / TiAlON / Si3N4 tandem absorber exhibited an ab-
sorptance of 0.95 and an emittance of 0.07. The absorptance
and the emittance were measured using a solar spectrum re-
flectometer and an emissometer, respectively. The source of
illumination was a tungsten-halogen lamp. The solar mea-
surement spectrum was achieved by monitoring the reflected
energy with four detectors that cover different wavelength
ranges. A weighted sum of the four detectors produced a
solar measurement spectrum. For the emittance measure-
ments, the emissometer detector was heated to 82 ° C. The
reflectometer and the emissometer were calibrated with stan-
dard samples.
The refractive index 共n兲 and the extinction coefficient 共k兲
of the tandem absorber, as measured using phase modulated
spectroscopic ellipsometry, are shown in Fig. 2. The n value
of TiAlN layer showed a minimum at ⬃500 nm and there-
after it increased with wavelength, whereas the k value in-
creased with wavelength. The increase in n and k values with
wavelength shows the metallic behavior of TiAlN.12 On the
other hand, for TiAlON layer, the n and k values decreased
with increasing wavelength. Low k values for the TiAlON
layer 共0.04–0.8兲 indicate its semitransparent behavior. These
data, thus, show that the TiAlON layer exhibits an interme-
diate character, i.e., a transition between the dielectric and
the metallic behavior, which is in agreement with the resis-
tivity data. The n value of Si3N4 was lower than those of
TiAlN and TiAlON and the extinction coefficient was zero
throughout the wavelength range. Since the k value of Si3N4
was zero, the absorptance of the tandem absorber can depend
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Appl. Phys. Lett. 89, 191909 共2006兲
only on the k values of the metal components in the TiAlN
and the TiAlON absorber layers. These results show that the
reflectance of the tandem absorber is reduced by gradually
increasing the refractive index from the surface to the sub-
strate, consequently increasing the absorption.
It is well known that a material with higher extinction
coefficient exhibits a higher absorptance. From the k values,
we calculated the absorption coefficient 共␤ = 4␲k / ␭兲. For
TiAlN layer, ␤ increased with increasing wavelength in the
visible region 共␤max = 3.2⫻ 106 cm−1兲 and decreased in the
IR region, indicating high absorption in the visible region.
On the other hand, for TiAlON, ␤ decreased with increasing
wavelength, indicating low absorption in the IR region. The
␤ value of Si3N4 was zero in both the visible and the IR
regions, thus confirming its transparent behavior. The ab-
sorption coefficient data thus suggest that TiAlN acts as the
main absorber layer.
The tandem absorber deposited on Cu substrate was heat
treated in air 共heating rate= 3 ° C / min兲 at temperatures in the
range TA = 200– 675 ° C for 2 h. The ␣ and ␧ values of the
tandem absorber did not change significantly after heat treat-
ment up to 600 ° C. For example, the tandem absorber ex-
hibited an ␣ = 0.92 共⌬␣ = 0.01兲 and an ␧ = 0.08 共⌬␧ = 0.02兲
after heat treatment at 600 ° C. For 675 ° C ⬎ TA ⬎ 600 ° C,
the emittance increased drastically which resulted in a de-
crease in the ␣ / ␧. This shows that the
Cu/ TiAlN / TiAlON / Si3N4 tandem absorber has a very high
thermal stability in air up to 600 ° C. These results were con-
firmed by micro-Raman spectroscopy measurements on the
FIG. 2. Experimentally determined n and k values of the
TiAlN / TiAlON / Si3N4 tandem absorber deposited on glass substrate, indi-
cating the graded refractive indices of the three layers.
191909-3 Barshilia et al.
FIG. 3. Raman spectra of the as-deposited TiAlN / TiAlON / Si3N4 tandem
absorber and coatings heat treated in air up to 900 ° C. The spectra showed
no changes in the acoustic and the optic modes up to 600 ° C, and the oxide
phases were observed only at 900 ° C.
heat-treated samples. The Raman data 共Fig. 3兲 showed no
significant changes in the nature of acoustic 共LA and TA,
150– 300 cm−1兲 and optic phonon 共LO and TO,
450– 650 cm−1兲 modes up to 600 ° C, indicating a stable mi-
crostructure of the tandem absorber.13 However, TiO2 and
Al2O3 phases were observed only at TA = 900 ° C for the tan-
dem absorber deposited on Si substrates 共dashed curve of
Fig. 3兲.
Annealing of Cu/ TiAlN / TiAlON / Si3N4 tandem ab-
sorber in air may induce several microstructural modifica-
tions such as interdiffusion, reaction between layers to pro-
duce a new phase, transformation within one or all layers,
and oxidation. These modifications result in changes in the
optical properties. The high thermal stability of the tandem
absorber of the present study is attributed to various factors.
Firstly, TiAlN acts as a diffusion barrier for Cu. Formation of
TiO, AlN, and Al5Ti2 compounds during annealing of
TiAlN / Cu at higher temperatures 共550 ° C兲 is reported to
Downloaded 08 Nov 2006 to 202.54.91.201. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
Appl. Phys. Lett. 89, 191909 共2006兲
effectively block the diffusion paths for Cu, thus making it
an ideal diffusion barrier layer.6 Secondly, the interdiffusion
between TiAlN / TiAlON and TiAlON / Si3N4 is expected to
be very low up to 600 ° C because of very high activation
energies, high melting points, and stable microstructures.
Due to these reasons the onset of defect mediated diffusion
and lattice diffusion is expected to be very high. Thirdly,
TiAlN, TiAlON, and Si3N4 exhibit very high oxidation resis-
tances, 750, 900, and 1400 ° C, respectively. The
TiAlN / TiAlON / Si3N4 tandem absorber, thus, exhibits high
thermal stability and retains its optical properties even at
higher operating temperatures.
In conclusion, we have shown that by varying the refrac-
tive indices and also the thicknesses of the component mate-
rials of the TiAlN / TiAlON / Si3N4 tandem absorber it is pos-
sible to achieve a solar absorber coating having a high solar
selectivity, which is stable in air up to 600 ° C.
The authors thank the director of NAL for giving per-
mission to publish these results. William Grips and N. T.
Manikandanath are thanked for help in the measurements of
absorptance and emittance and Raman spectroscopy data.
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