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Article history: Triple-layer broadband abrasion-resistant antireflective (AR) coatings with excellent transmittance at
TM
Received 31 May 2012 400–800 nm were designed with the aid of thin film design software (TFCalc ). SiO2, TiO2 and SiO2–
Received in revised form TiO2 hybrid thin films with refractive indices of 1.44, 2.20 and 1.71 for the up, middle and bottom
21 December 2012
layers, were dip-coated from SiO2, TiO2 and SiO2–TiO2 hybrid sols by sol–gel process, respectively. SiO2
Accepted 21 December 2012
and TiO2 sols were prepared using tetraethyl orthosilicate (TEOS) and tetrabutyl orthotitanate (TBOT)
Available online 4 February 2013
as precursors and hydrochloric acid as catalyst. These designed triple-layer broadband AR coatings with
Keywords: an average transmittance as high as 98.4% at visible region were successfully obtained. Hexamethyldi-
Broadband antireflective coating silazane (HMDS) was further used to modify the surface of the AR coatings, which greatly improved the
Sol–gel process
hydrophobicity of the coatings, and thus gave the AR coatings some self-cleaning property. These triple-
Hydrophobicity
layer abrasion-resistant broadband AR coatings with excellent transmittance in the visible region have
Thin film design
Abrasion-resistance potential value in the field of solar cells.
& 2013 Elsevier B.V. All rights reserved.
0927-0248/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.solmat.2012.12.037
L. Ye et al. / Solar Energy Materials & Solar Cells 111 (2013) 160–164 161
2.3. Characterization
concentration of SiO2 was 3% by weight. The resultant sol was ples were followed during TFCalc program calculation: (1) The
aged in a sealed glass container at 30 1C for 7 days and then optical thickness for up, middle and bottom layers are set to l/4,
filtered through a 0.22 mm PVDF filter prior to use. l/2 and l/4; (2) Because of its low refractive index and excellent
abrasion-resistance, acid-catalyzed silica is chosen as the up
2.1.2. Preparation of TiO2 sol layer; (3) As the refractive index of up layer is given, the
A solution of TBOT, C2H5OH, H2O and HCl was first prepared optimization steps are to determine the optimum refractive
and stirred for 2 h at 30 1C. The molar ratio of TBOT:H2O:- indices of the middle and bottom layer by computer program.
C2H5OH:HCl was 1:3.55:49.75:0.22 and the final concentration As examples, several triple-layer coatings design and the
of TiO2 was 3% by weight. The resultant sol was aged in a sealed corresponding theoretical transmittances are shown in Table 1.
glass container at 30 1C for 7 days and then filtered through a C2 design gives an optimum result.
0.22 mm PVDF filter prior to use.
3.2. Experimental preparation of the triple-layer broadband AR
2.1.3. Preparation of SiO2–TiO2 Hybrid sols coatings
SiO2 sol and TiO2 sol were mixed with various weight ratios
and stirred for 2 h at 30 1C. The mixed sols were aged in sealed Table 2 shows the refractive indices and film thickness of the
glass containers at 30 1C for 7 days. The hybrid sols were finally computer designed optimum triple-layer broadband AR coatings,
filtered through a 0.22 mm PVDF filter prior to use. and the corresponding theoretical transmittance spectrum is
162 L. Ye et al. / Solar Energy Materials & Solar Cells 111 (2013) 160–164
Table 1
The parameters of the l/4 l/2 l/4 triple-layer AR coatings on glass (l0 ¼ 550 nm).
Table 2
The parameters of the theoretical and experimental triple-layer AR coatings
on glass.
Fig. 3. The refractive indices of SiO2–TiO2 hybrid film as a function of weight ratio
of silica.
the triple-layer AR coating. Fig. 2 also indicates that the experi- 3.5. Mechanical performance
mental transmittance spectrum is in good agreement with our
TM
previous theoretical design by the TFCalc program. The trans- For outdoors use, the abrasion-resistance is very important for AR
mission difference in the short-wavelength regions is probably coatings because they have to endure abrasion process due to
due to the dispersion of the refractive index in the wavelength atmospheric conditions and cleaning processes. The decrease of the
region [12,25]. In the theoretical design it has been assumed that average transmittance in the visible region was adopted to evaluate
the refractive index of films and substrate did not change with the abrasion-resistance of the AR coatings after being rubbed with
wavelength and the refractive index at 550 nm was adopted as abrasion-resistance test equipment. As shown in Fig. 6, the AR
the refractive index for the entire visible region. Actually, the performance of the coating remains almost intact, with only a 0.2%
refractive index of titania and silica increases with the decrease of reduction in the region of 400–800 nm, indicating an excellent
the wavelength, which leads to the differences between the abrasion-resistant property of this triple-layer AR coating. The excel-
experimental and designed transmittance spectra. lent abrasion-resistance achieved is an anticipated result of the
upfront film design. The film materials used in this work are the
3.4. Morphology of the coatings sol–gel silica and titania which are robust and condense. In particu-
larly, the growth of silica sol with an acid catalyst results in a
The microscopic structure of the triple-layer coatings, obtained by structure of linear chains which leads to a high abrasion-resistance
SEM, is shown in Fig. 4. From the cross-sectional image of the triple- with high adhesive force on substrates [24,27]. Furthermore, the
layer coatings, we can find that the borders between any two of the adhesion of the coatings was examined by a tape test [20]. The tape
three layers are apparent, indicating no interpenetration among the (Brand Panda) was laid across the coated surface, and then was
interfaces of the layers. Fig. 5 shows the surface morphologies of slowly pulled away. The AR properties showed no change after
single-layer acid catalyzed SiO2 coating and the triple-layer coatings, peeling of the tape, which indicates good adhesion among individual
the root-mean-square (RMS) roughness (Rq) for the single-layer silica layers and the glass substrate.
coating is 0.81 nm and reaches to 1.87 nm for triple-layer broadband
AR coating, which is probably due to the accumulation of the 3.6. Hydrophobic treatment of triple-layer AR coatings with HMDS
roughness for the three layers. Even with a considerable increase in
roughness, this roughness value for the triple layers coating is still The hydrophobicity of AR coatings used in solar cells is also
small to cause any intense surface light scattering [26]. important in preventing contaminants. A very hydrophobic surface
can afford the AR coating some self-cleaning property, because the
water can easily roll and take away the contaminants from the
hydrophobic surface [28]. Hydrophobicity is generally characterized
by water contact angle measurement, and an increase in the value
of water contact angle indicates a more hydrophobic surface.
The acid-catalyzed silica film is hydrophilic due to the many
hydroxyl groups on silica film surface. The hydrophobicity of the
surface can be significantly improved by replacing the polar
hydroxyl groups with nonpolar groups by surface modification.
Fig. 7 shows the variation in water contact angle of the AR
coatings as a function of HMDS concentration in C2H5OH solution.
It is clearly that the HMDS treatment improves dramatically the
water contact angle of the AR coatings. The increase in hydro-
phobicity is caused by the introduction of –OSi(CH3)3 groups into
the surfaces of the AR coatings [29].
4. Conclusions
Fig. 5. AFM patterns of the single-layer acid catalyzed SiO2 coating (a) and the triple-layer coating (b).
164 L. Ye et al. / Solar Energy Materials & Solar Cells 111 (2013) 160–164