Porous anodic alumina with low refractive index for

broadband graded-index antireflection coatings

Junwu Chen,
1
Biao Wang,
1,
* Yi Yang,
1
Yuanyuan Shi,
1
Gaojie Xu,
1,2
and Ping Cui
1
1
Ningbo Institute of Material Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China
2
e-mail: xugj@nimte.ac.cn
*Corresponding author: wangbiao@nimte.ac.cn
Received 2 July 2012; revised 29 August 2012; accepted 3 September 2012;
posted 4 September 2012 (Doc. ID 171666); published 27 September 2012
Materials with very low refractive index are essential to prepare broadband graded-index antireflection
(AR) coatings. However, the availability of such materials is very limited. In this study, large-area
(4 cm 4 cm) low refractive index porous anodic alumina (PAA) coatings on glass substrate were pre-
pared successfully by electron-beam evaporation, electrochemical oxidation, and chemical etching
method. The nanopore size of PAA film is smaller than 40 nm, and the refractive index of PAA film
is n 1.08. Besides, five-layered graded-index broadband PAA coatings with refractive indices following
the Gaussian profile were also prepared to noticeably eliminate the reflectance of glass over a broadband
wavelength, and the lowest reflectivity is 0.64% at the wavelength of 534 nm at normal incidence. The
PAA AR coatings having an omnidirectional nature are likely to have practical applications in photo-
voltaic cells and optical devices. 2012 Optical Society of America
OCIS codes: 220.4241, 310.1210, 310.4165, 310.6860.
1. Introduction
It is well known that reflections will inevitably ap-
pear when light propagates across an interface of
two mediums with different refractive indices. The
graded-index antireflection (AR) coatings whose re-
fractive indices gradually change from one medium
to the other medium can effectively suppress the re-
flection and increase the light transmission of the
optical devices [1,2]. One of the common ambient
mediums is air, whose refractive index is 1.0. How-
ever, optical materials with very low refractive indices
(low-n) that closely match the refractive index of air
are difficult to obtain. Particularly for dense materi-
als, refractive indices of 1.10 or 1.20 do not exist.
Therefore, porous nanomaterials with low refractive
index are often used for preparing graded-index
AR coatings.
Different methods of making graded-index AR
coatings have been reported, including lithography
and wet etching [3], sol-gel process [4], integrated
nanoisland coating arrays on nano-conical-frustum
arrays [5], improved metal-induced chemical etching
[6], and oblique-angle deposition [7,8]. At present,
the lowest refractive index n 1.05 was reported
by Xi and Schubert et al. [7] using oblique-angle de-
position, and their study showed that oblique-angle
deposition has good control over the refractive index
profile when the substrates are flat. The preparation
of graded-index AR coatings on uneven surfaces is
rarely reported.
Porous anodic alumina (PAA) formed by electro-
chemical oxidation has been investigated for many
years [9] and been widely used as templates for
fabrication of nanowires or nanotubes [1012]. The
nanopores in PAA are independent and can be en-
larged easily in acid solution, so the refractive in-
dices of PAA films can be controllably varied and a
very low refractive index can be reached. In this
study, large-area (4 cm 4 cm) low-n PAA coatings
on glass substrate were prepared by combination
of electron-beam evaporation, electrochemical oxida-
tion, and chemical etching methods. Furthermore,
1559-128X/12/286839-05$15.00/0
2012 Optical Society of America
1 October 2012 / Vol. 51, No. 28 / APPLIED OPTICS 6839
five-layered graded-index AR coatings with refrac-
tive indices following a Gaussian profile were suc-
cessfully prepared on flat and patterned glasses,
respectively.
2. Experimental Details
Ultra clear glass substrates (the thickness is 2 mm
and the size is 4 cm 4 cm) were cleaned by ultraso-
nication in detergent, acetone, deionized water, and
ethanol successively. Pure Al (99.99%) films with
thickness 850 nm were deposited onto glass by
electron-beam evaporation in a vacuum of 10
5
Pa
(MUE-ECO-EB, ULVAC Technologies. Inc.). Then
the coated glasses were anodized at 20 V in 0.3 M
oxalic solutions at 5C. Next, the anodized films were
immersed in 5 wt. % H
3
PO
4
solutions at 30C for a
predetermined time to adjust the pore diameter. Fi-
nally, the samples were annealed in the air at 550C
for 5 h.
The wavelength dependence reflectivity was
measured by a spectrophotometry (Perkin Elmer,
Lambda 950) at incident angle of 8, and the incident
angle dependence reflectivity was measured by
ellipsometry (M-1500DI, J. A. Woollam). The surface
and the cross-section scanning electron microscopy
(SEM) images were characterized by field-emission
scanning electron microscopy (FE-SEM, HITACHI
S-4800) operated at 5 kV.
3. Results and Discussion
Figure 1 shows a surface SEM image of the low-n
PAA on glass acid etched at 30C for 28 min. From
Fig. 1 we can see that the nanopore diameter is about
40 nm and the thickness of pore wall is less than
10 nm. The refractive index of PAA film measured
by ellipsometry is n 1.08, which confirms the por-
ous nanostructure observed in Fig. 1. Furthermore,
the nanopore size is much smaller than the wave-
length of visible light, so Mie and Rayleigh scattering
can be neglected over the visible spectrum. Next,
we will show that the low-n PAA film was used in
preparing graded-index AR coatings and virtually
eliminates Fresnel reflection.
Figure 2(a) shows three different graded-index
profiles with linear, quintic, and Gaussian profiles
that have index matching with air and a glass sub-
strate with refractive index of n
s
1.5. Figures 2(b)
and 2(c) show the calculated reflectance for these
graded-index profiles depending on spectral and an-
gular, respectively. All of the three profiles have good
performance with low reflectivity for both transverse
electric (TE) and transverse magnetic (TM) polariza-
tions over a broad wavelength [Fig. 2(b)] and angle-
of-incidence range [Fig. 2(c)]. Moreover, it is easy to
find out that the Gaussian index profile has the best
performance, with R < 0.1% for the spectrum from
300 to 1500 nm and the angle from 0 to 60.
Therefore, the Gaussian index profile is the optimum
profile, which is in consistent with the previous
conclusion reached by Chen [13].
Figure 3 shows the preparation processes of
graded-index PAA films designed following the
Gaussian index profile. First, pure Al (99.99%) film
was evaporated on the glass using electron-beam
evaporation. Then the Al film was anodized in oxalic
Fig. 1. Surface SEM image of the low-n PAA coating.
Fig. 2. (Color online) Different index profiles for graded-index
coating. (a) Linear, quintic index, and Gaussian profiles for a sub-
strate of glass with n
s
1.5. (b) Calculated wavelength-dependent
reflectance for linear, quintic index, and Gaussian profiles at inci-
dent angle of 8. (c) Calculated angular-dependent reflectance for
linear, quintic index, and Gaussian profiles at wavelength 600 nm.
The calculation is approximated by Essential Macleod using 100
layers of equal thickness.
6840 APPLIED OPTICS / Vol. 51, No. 28 / 1 October 2012
acid to form the first PAA layer and immersed into
H
3
PO
4
solution to enlarge the nanopores in the first
PAA layer. After careful cleaning with deionized
water, the sample was anodized again to form the
second PAA layer and immersed in acid solution
again to enlarge the nanopores both in the first and
second PAA layers. By repeating the anodization and
acid etching process for five times, graded-index PAA
films composed of five layers were finally completed.
By adjusting the time of anodization and acid etch-
ing, we can control the refractive index and thickness
of each PAA layer easily. The parameters of prepara-
tion processes are list in Table 1.
Figure 4 is the cross-sectional SEM picture of the
PAA film prepared based on the above processes. The
refractive index of each layer measured by ellipsome-
try and the thickness determined according to SEM,
are listed in Table 1. Because the five-layer structure
was too complex to estimate the refractive indices of
the layers precisely, we prepared five single-layer
samples and then measured the refractive indices
of the layers individually. The measured refractive
index of the top layer is 1.08, which is very low and
close to the index of air. The bottom layer is 1.47,
which closely matches the index of glass. Figure 4
clearly shows that the PAA film is composed of five
layers and the nanopore diameter of each layer de-
creases gradually from top to bottom. Furthermore,
the thickness and refractive index of each layer is
well matched with the Gaussian profile, as shown
in Fig. 4. Therefore, the PAA nanostructure matches
the refractive indices of air and the substrate and has
excellent AR characteristic.
More importantly, our method could prepare the
AR films not only on flat substrates but also on
patterned substrates. Figure 5 is a photograph of
graded-index PAA coating on two different sub-
strates, the left is flat substrate while the right is
patterned substrate (the shape of the pattern is in-
verted pyramid and the depth of the pattern is about
0.3 mm), showing clearly both samples possessed
very good transparency. In particular, the graded-
index PAA coatings on both substrates are almost
neutral colors, which means the interference colors
Fig. 3. Schematic illustration of the preparation processes of
graded-index PAA films consist of five layers.
Table 1. Time of Electrochemical Oxidation, Time of Chemical Etching,
Measured Thickness, and Measured Refractive Index of the AR Film
Graded-
Index
Layer
Number
Anodization
Time
(min)
Etching
Time
(min)
Measured
Thickness
(nm)
Measured
Refractive
Index
1 25 5 504 1.08
2 6 5 149 1.18
3 5.5 7 133 1.33
4 5 11 108 1.41
5 5 0 103 1.47
Fig. 4. Cross-sectional SEM image of graded-index coating
with a Gaussian index profile. The coating consists of five porous
anodic alumina layers whose porosity increases progressively from
substrate to air.
Fig. 5. (Color online) Optical photograph of graded-index PAA
coating on the flat (left) and patterned (right) surfaces of glass.
The inset is the high magnification image of the boxed area.
The rule is in centimeters.
1 October 2012 / Vol. 51, No. 28 / APPLIED OPTICS 6841
often with glass coatings have almost been elimi-
nated. It is also clear that the patterned glass coated
with PAA film performs as well as the flat one.
Both experimental and theoretical results are
shown in Fig. 6. Figure 6(a) shows the wavelength
dependence reflectivity of ultra clear glass with
PAA coatings on both sides at incident angle of 8.
We can see the shape of measured and calculated
curves in Fig. 6(a) are similar, having wave peak
at the wavelength about 400 nm, having wave trough
at the wavelength about 500 nm, and starting to
rise at the wavelength above 900 nm. For each peak
in calculated curve, there are two corresponding
peaks in the measured curve and this may be caused
by the tiny structural difference between the two
PAA coatings on glass. The electrolytic cell used in
this study has only an anode and a cathode, so the
PAA coating on the backside has to be fabricated
after the preparation of PAA coating on the front
of the glass. In this case, the PAA coating on the front
of glass will experience extra acid solution soak and
heat treatment, which will cause slight structural
difference in the two PAA coatings. The lowest mea-
sured reflectivity of the PAA coated glass sample is
0.64% while the reflectivity of reference glass with-
out coating is 8.73% at the wavelength of 534 nm.
Figures 6(b) and 6(c) show measured and calculated
results for TM and TE polarization, respectively. The
measured and calculated results are in good agree-
ment and the two curves coincide with each other
especially below the angle of 60. The spectral de-
pendence and angular dependence of the reflectance
curves demonstrate that our graded-index AR coat-
ings based on PAA nanostructure have the broad-
band omnidirectional characteristic.
4. Conclusion
In conclusion, large-area low-n PAA coatings on
glass substrates were successfully prepared by com-
bination of electron-beam evaporation, electrochemi-
cal oxidation, and chemical etching methods. The
lowest refractive index is n 1.08. Furthermore,
five-layered graded-index broadband PAA coatings
with refractive indices designed following the
Gaussian profile were also successfully prepared.
The graded-index PAA coatings have a broadband
omnidirectional nature, and the lowest reflectivity
of PAA coated glass sample is R 0.64% at the wa-
velength of 534 nm.
This work was supported by the National Basic
Research Program of China (2009CB930801), Ningbo
Natural Science Foundation (2010A610158), the
National Natural Science Foundation of China
(11204325, 21003145), Zhejiang Provincial Natural
Science Foundation of China (D4080489), the CAS/
SAFEA International Partnership Program for Crea-
tive Research Teams, Science and Technology Innova-
tive Research Team of Zhejiang Province and Ningbo
Municipality (2009B21005).
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