Solar Energy Materials & Solar Cells 111 (2013) 160164

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Solar Energy Materials & Solar Cells

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Solgel preparation of SiO2/TiO2/SiO2TiO2 broadband antireective coating for solar cell cover glass
Longqiang Ye a, Yulu Zhang a, Xinxiang Zhang a, Teng Hu a, Rui Ji a, Bin Ding b, Bo Jiang a,n
a b

Key Laboratory of Green Chemistry & Technology, College of Chemistry, Sichuan University, Chengdu 610064, China Research Institute of Petroleum Exploration and Development of PetroChina, Beijing 100083, China

a r t i c l e i n f o
Article history: Received 31 May 2012 Received in revised form 21 December 2012 Accepted 21 December 2012 Available online 4 February 2013 Keywords: Broadband antireective coating Solgel process Hydrophobicity Thin lm design Abrasion-resistance

a b s t r a c t
Triple-layer broadband abrasion-resistant antireective (AR) coatings with excellent transmittance at TM 400800 nm were designed with the aid of thin lm design software (TFCalc ). SiO2, TiO2 and SiO2 TiO2 hybrid thin lms with refractive indices of 1.44, 2.20 and 1.71 for the up, middle and bottom layers, were dip-coated from SiO2, TiO2 and SiO2TiO2 hybrid sols by solgel process, respectively. SiO2 and TiO2 sols were prepared using tetraethyl orthosilicate (TEOS) and tetrabutyl orthotitanate (TBOT) as precursors and hydrochloric acid as catalyst. These designed triple-layer broadband AR coatings with an average transmittance as high as 98.4% at visible region were successfully obtained. Hexamethyldisilazane (HMDS) was further used to modify the surface of the AR coatings, which greatly improved the hydrophobicity of the coatings, and thus gave the AR coatings some self-cleaning property. These triplelayer abrasion-resistant broadband AR coatings with excellent transmittance in the visible region have potential value in the eld of solar cells. & 2013 Elsevier B.V. All rights reserved.

1. Introduction Photovoltaic power has been getting more and more important due to the growing depletion of oil resources and increasing environmental consciousness. In the industries of solar cells, photovoltaic devices are located outdoors; therefore glass covers are essential for preventing damage from physical shock and corrosion. There are, however, approximately 8% reection on two surfaces of the cover glass since the refractive index of cover glass is around 1.52 while that of air is 1.0. The introduction of antireective (AR) coatings can effectively reduce these losses and thereby improve the efciency of the solar cells. AR coatings derived from solgel process have attracted much interest due to their advantages of low cost, simple operation process and controllable microstructure, and been widely applied in energyrelated applications [16]. AR coatings used in solar cells must be high abrasionresistance to endure the outdoor conditions and cleaning processes. The acid catalyzed silica sol derived coating is an ideal material due to its low refractive index, excellent abrasionresistance and good durability. Titania coating is transparent to visible light with high refractive index and low absorption properties. Consequently, the acid catalyzed silica and titania coatings are very convenient materials for AR coatings in solar

Corresponding author. Tel.: 86 28 85418112; fax: 86 20 85412907. E-mail address: jiangbo@scu.edu.cn (B. Jiang).

cells [710]. For a quarter-wave (l/4) AR coating having a refractive index equal to the square root of refractive index of substrates, the transmittance can be reached as high as 100% at the given wavelength. However, the average transmittance is low in the entire visible region; this short back restricts their real applications in the eld of solar cells. Double-layer or multi-layer broadband AR coatings have been also designed and prepared [11,12] to reach a relatively high average transmittance in the visible region. In solar cells, the glass cover is an essential component as important as silicon wafer. The preparation of AR coatings with both excellent optical performance and abrasion-resistance on silicon wafer has been widely reported [1317,12] while these coatings on cover glass receive relatively less attention. The glass cover has a relatively low refractive index of about 1.52, and based on optical theory and by considering available lm materials, the preparation of AR coatings on substrates with low refractive index is much harder than on substrates with relatively high refractive index due to the absence of robust lm materials with low refractive index [18]. l/4l/4 and l/4l/2 double-layer AR coatings have been reported for low refractive index substrate [19,20], but these coatings cannot balance the abrasion-resistance and broadband transmittance at visible region very well. Multilayer AR coatings become then a good choice. In 1940s, Lockhart and King described a l/4l/2l/4 triple-layer broadband AR coating which possessed satised transmittance at visible region [21]. However, due to the limit of available lm materials at that time, they did not succeed to optimize the refractive indices

0927-0248/$ - see front matter & 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.solmat.2012.12.037

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2.2. Preparation of AR coatings Borosilicate glasses were cleaned by ultrasonication in acetone for 10 min, then wiped carefully with cleanroom wipers and dried under a stream of compressed air prior to the deposition of the triple-layer AR coatings. SiO2TiO2 sol, TiO2 sol and SiO2 sol were deposited on both sides of the well-cleaned substrates sequentially at a relative humidity less than 20% by dip coating at withdrawal rate 175 mm/min, 500 mm/min and 160 mm/min, respectively. The triple-layer coatings were heated at 200 1C for 8 h. The surfaces treatment of the coatings were carried out by immersing the coated samples into HMDS/C2H5OH solutions with different concentrations for 48 h and then dried at 160 1C. 2.3. Characterization Theoretical transmittance spectrum of triple-layer AR coating TM was simulated with TFCalc program (Software Spectra Inc), and the experimental transmittance spectrum was measured with an UVvis spectrophotometer (Mapada, UV-3100PC). Surface morphologies and cross-sections of the AR coating were investigated separately by atomic force microscopy (AFM) (SEIKO SPA-400) and JSM-5900LV scanning electrons microscope (SEM). The refractive indices of the coatings were determined by ellipsometry (SENTECH SE850 UV). The mechanical durability of the resultant coatings was assessed in the abrasion test, in which the standard normal stress 25 kPa was applied with rotational shear (100 rpm for 0.5 h) on an abrasion-resistance machine (DZ-8103, Dongguan City Dazhong Instrument CO, LTD.). The mechanical damages were determined by the change of the average transmittance over the visible spectrum before and after the abrasion test. Water contact angles DSA100 (Germany) instrument at room were measured with a Kruss temperature.

Fig. 1. The procedure of preparation of SiO2, TiO2 and SiO2TiO2 hybrid sols.

of three layers. Precedent studies have shown that silica/titania hybrid lm with refractive index varying from 1.44 to 2.20 can be obtained by mixing silica and titania sols together [22,23]. In this work, we tried to optimize Lockharts triple-layer AR coating by investigating effect of refractive index of three layers on the average transmittance and broadband property with the TM aid of thin lm design software (TFCalc ), and an optimum triplelayer broadband AR coating on solar cell cover glass was designed having an average transmittance of 99.1% in the visible region of 400800 nm. Then this SiO2/TiO2/SiO2TiO2 triple-layer coating with an average transmittance of more than 98.4% was successfully prepared by the solgel process.

3. Results and discussion 3.1. Computer-aid design of triple-layer broadband AR coatings Optical properties of antireective coatings can be monitored by many methods, such as vector method, admittance loci, and so on. The computer-aid design is preferred because it is fast and straightforward. In this work, the triple-layer AR coating was TM optimized using the TFCalc program. As the commonly used solgel lms are silica, titania and silica/titania hybrid lms with refractive index varying from 1.44 to 2.20, we have tried to optimize the triple-layer AR coating with refractive index of individual layer ranging from 1.44 to 2.20. The following princiTM ples were followed during TFCalc program calculation: (1) The optical thickness for up, middle and bottom layers are set to l/4, l/2 and l/4; (2) Because of its low refractive index and excellent abrasion-resistance, acid-catalyzed silica is chosen as the up layer; (3) As the refractive index of up layer is given, the optimization steps are to determine the optimum refractive indices of the middle and bottom layer by computer program. As examples, several triple-layer coatings design and the corresponding theoretical transmittances are shown in Table 1. C2 design gives an optimum result. 3.2. Experimental preparation of the triple-layer broadband AR coatings Table 2 shows the refractive indices and lm thickness of the computer designed optimum triple-layer broadband AR coatings, and the corresponding theoretical transmittance spectrum is

2. Experimental details 2.1. Preparation of sol Fig. 1 shows the procedure of the preparation of SiO2, TiO2 and SiO2TiO2 hybrid sols. 2.1.1. Preparation of SiO2 sol A solution of TEOS, C2H5OH, H2O and HCl was rst prepared and stirred for 2 h at 30 1C. The molar ratio of TEOS: H2O: C2H5OH: HCl was 1: 4.01: 36.83: 4.16 10 3 [24] and the nal concentration of SiO2 was 3% by weight. The resultant sol was aged in a sealed glass container at 30 1C for 7 days and then ltered through a 0.22 mm PVDF lter prior to use. 2.1.2. Preparation of TiO2 sol A solution of TBOT, C2H5OH, H2O and HCl was rst prepared and stirred for 2 h at 30 1C. The molar ratio of TBOT:H2O:C2H5OH:HCl was 1:3.55:49.75:0.22 and the nal concentration of TiO2 was 3% by weight. The resultant sol was aged in a sealed glass container at 30 1C for 7 days and then ltered through a 0.22 mm PVDF lter prior to use. 2.1.3. Preparation of SiO2TiO2 Hybrid sols 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 glass containers at 30 1C for 7 days. The hybrid sols were nally ltered through a 0.22 mm PVDF lter prior to use.

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Table 1 The parameters of the l/4 l/2 l/4 triple-layer AR coatings on glass (l0 550 nm). Bottom layer Refractive index (n1) C1 C2 C3 C4 C4 C5 1.61 1.71 1.81 1.71 1.61 1.81 Film thickness (d1)/nm 85 80 76 80 85 76 Middle layer Refractive index (n2) Film thickness (d2)/nm 125 125 125 131 131 120 Up layer Refractive index (n3) 1.44 1.44 1.44 1.44 1.44 1.44 Film thickness (d3)/nm 95 95 95 95 95 95 98.6 99.1 98.4 99.0 98.9 98.7 The average transmittance (400800 nm)/%

2.20 2.20 2.20 2.10 2.10 2.30

Table 2 The parameters of the theoretical and experimental triple-layer AR coatings on glass. Theoretical parameter (C2) Refractive index Film thickness/ nm 80 125 95 Experimental parameter Dip-coating speed (mm/min) Refractive index Film thickness/ nm 84 128 86 175 500 160

Cover glass Bottom layer Middle layer Up layer

1.52 1.71 2.20 1.44

1.52 1.71 2.20 1.44

Fig. 3. The refractive indices of SiO2TiO2 hybrid lm as a function of weight ratio of silica.

Fig. 2. Theoretical and experimental transmission spectra of the triple-layer AR coating.

varying from 1.44 to 2.20 have been obtained by mixing the starting silica and titania sols together in different proportions. Fig. 3 shows the effect of weight ratio of silica on the refractive index of silica/tatania hybrid lm. The refractive index of the hybrid lm is proportional to the weight ratio of silica in the hybrid sols. The bottom layer with refractive index of 1.71 can be obtained when the silica weight ratio is about 50%. The lm thickness is another important factor inuencing the optical properties of the AR coating, which can be easily controlled by varying the sol concentration and/or the dip-coating speed in the solgel process. For a sol with given concentration, it is convenient to control the lm thickness by changing dipcoating speed. As a result of a series of experiments, Table 2 gives the optimized dip-coating speed for individual layers, which are 175 mm/min, 500 mm/min and 160 mm/min for bottom, middle and up layers, corresponding to the lm thickness of 84 nm, 128 nm and 86 nm, respectively, which showed that the lm thickness can be controlled with reasonable accuracy. 3.3. Optical property of the triple-layer AR coating The silica/titania hybrid, titania and silica lms were then deposited successively on the glass substrate by dip-coating method to form the triple-layer broadband AR coatings. Fig. 2 shows the experimental and theoretical transmittance spectra of triple-layer broadband AR coating as well as the experimental transmittance of glass substrate. The average transmittance of the experimental triple-layer AR coating in the region of 400800 nm is 98.4%. Compared to the transmittance of the glass substrate of 92.0%, an enhancement of 6.4% in transmittance is achieved with

given in Fig. 2. The theoretical average transmittance in the visible region can reach up to 99.1%. Accurate control of the refractive index (n) and lm thickness (d) of the individual layers is the key factor to achieve the right multi-layer AR coating. As shown in Table 2, the refractive indices required for up, middle and bottom layers are 1.44, 2.20 and 1.71, respectively. The silica layer with n 1.44 and titania layer with n 2.20 were used as the up and middle layers, then it remains to nd a lm material with a refractive index of 1.71 to use as the bottom layer. solgel process provides a convenient route for preparation of hybrid materials with accurate stoichimetric ratio. In this work, silica/titania hybrid lms with refractive index

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the triple-layer AR coating. Fig. 2 also indicates that the experimental transmittance spectrum is in good agreement with our TM previous theoretical design by the TFCalc program. The transmission difference in the short-wavelength regions is probably due to the dispersion of the refractive index in the wavelength region [12,25]. In the theoretical design it has been assumed that the refractive index of lms and substrate did not change with wavelength and the refractive index at 550 nm was adopted as the refractive index for the entire visible region. Actually, the refractive index of titania and silica increases with the decrease of the wavelength, which leads to the differences between the experimental and designed transmittance spectra. 3.4. Morphology of the coatings The microscopic structure of the triple-layer coatings, obtained by SEM, is shown in Fig. 4. From the cross-sectional image of the triplelayer coatings, we can nd that the borders between any two of the three layers are apparent, indicating no interpenetration among the interfaces of the layers. Fig. 5 shows the surface morphologies of single-layer acid catalyzed SiO2 coating and the triple-layer coatings, the root-mean-square (RMS) roughness (Rq) for the single-layer silica 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 roughness for the three layers. Even with a considerable increase in roughness, this roughness value for the triple layers coating is still small to cause any intense surface light scattering [26].

3.5. Mechanical performance For outdoors use, the abrasion-resistance is very important for AR coatings because they have to endure abrasion process due to atmospheric conditions and cleaning processes. The decrease of the average transmittance in the visible region was adopted to evaluate the abrasion-resistance of the AR coatings after being rubbed with abrasion-resistance test equipment. As shown in Fig. 6, the AR performance of the coating remains almost intact, with only a 0.2% reduction in the region of 400800 nm, indicating an excellent abrasion-resistant property of this triple-layer AR coating. The excellent abrasion-resistance achieved is an anticipated result of the upfront lm design. The lm materials used in this work are the solgel silica and titania which are robust and condense. In particularly, the growth of silica sol with an acid catalyst results in a structure of linear chains which leads to a high abrasion-resistance with high adhesive force on substrates [24,27]. Furthermore, the adhesion of the coatings was examined by a tape test [20]. The tape (Brand Panda) was laid across the coated surface, and then was slowly pulled away. The AR properties showed no change after peeling of the tape, which indicates good adhesion among individual layers and the glass substrate. 3.6. Hydrophobic treatment of triple-layer AR coatings with HMDS The hydrophobicity of AR coatings used in solar cells is also 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 lm is hydrophilic due to the many hydroxyl groups on silica lm surface. The hydrophobicity of the surface can be signicantly improved by replacing the polar hydroxyl groups with nonpolar groups by surface modication. 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 hydrophobicity is caused by the introduction of OSi(CH3)3 groups into the surfaces of the AR coatings [29].

4. Conclusions Triple-layer broadband antireective (AR) coating with average transmittance of 99.1% was designed by computer-aid calculation.

Fig. 4. The cross-sectional SEM photograph of the triple-layer coating.

Fig. 5. AFM patterns of the single-layer acid catalyzed SiO2 coating (a) and the triple-layer coating (b).

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[3]

[4]

[5]

[6]

[7] [8]

[9] Fig. 6. Change in transmittance of AR coatings before and after abrasion. [10]

[11] [12]

[13]

[14]

[15] [16] [17]

Fig. 7. Water contact angle versus concentration of HMDS.

[18]

Silica/titania hybrid lm with refractive index varying from 1.44 to 2.20 was prepared by the solgel process and applied as lm materials for the triple-layer broadband AR coating. SiO2/TiO2/SiO2 TiO2 triple-layer AR coating with an average transmittance of 98.4% in the visible region was successfully achieved using solgel dip coating method. The hydrophobicity of AR coating can be signicantly improved by surface modication with HMDS. This triplelayer abrasion-resistant broadband AR coating with excellent transmittance in the visible region and improved self-cleaning property has potential value in the eld of solar cells.

[19]

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Acknowledgment
[25]

The authors gratefully acknowledge the support from China National Petroleum and Gas Corporation science and technology development project Nano intelligent chemical agent (2011A1001). References

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