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Materials Letters 62 (2008) 577 580 www.elsevier.com/locate/matlet

Diamond-like carbon protective anti-reflection coating for Si solar cell

Won Seok Choi a,b , Kyunghae Kim a , Junsin Yi a , Byungyou Hong a,b,
a

School of Information and Communication Engineering, Sungkyunkwan University, Suwon 440-746, South Korea b Center for Advanced Plasma Surface Technology, Sungkyunkwan University, Suwon 440-746, South Korea Received 5 December 2004; accepted 1 June 2007 Available online 16 June 2007

Abstract Diamond-like carbon (DLC) films were deposited on corning glass and silicon substrates by the RF-PECVD (Plasma Enhanced Chemical Vapor Deposition) method using methane (CH4) and hydrogen (H2) gases. We examined the effects of the CH4 to H2 ratio on the tribological and optical properties of the DLC films. The hardness of the DLC films was measured with a nano-indenter. The optical properties of the DLC thin film were investigated by UV/VIS spectrometry and ellipsometry. From these measurements, we obtained optimum anti-reflection coating at a methane flow rate of 20 sccm. Also, solar cells were fabricated on a silicon substrate using the optimized DLC films as an anti-reflection coating and we obtained an increase of solar cell efficiency of about 20%. 2007 Elsevier B.V. All rights reserved.

1. Introduction Diamond-like carbon (DLC) films have found several important applications in the fields of optics, electricity [1,2], solid state devices, etc., due to their exceptional properties such as their high hardness, high electrical resistivity, low infrared (IR) absorption, transparency to visible light and chemical inertness. Because DLC films have wide bandgaps and adjustable refractive indices, they can be utilized as protective coatings for IR windows and as anti-reflective coatings for solar cells [3,4]. Various physical and chemical methods have been employed to synthesize DLC films, such as sputtering [5], pulsed laser deposition [6], plasma-enhanced chemical vapor deposition [2,7], and filtered vacuum arc [8]. Among these methods, the radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) method is widely used for the synthesis of DLC thin films, because it uses standard plasma processing technology that allows the simple and relatively inexpensive low-temperature coating of a range of temperature sensitive substrates over a large area and allows for the uniform coating of substrates having different shapes and sizes [9].

In the case of DLC (a-C:H) films, the hydrogen content in the film has an important effect on the DLC properties. This is because hydrogen atoms terminate the dangling bonds of the amorphous carbon so as to improve the properties of the DLC films, while the hydrogen content controls their optical bandgap. In this work, we used the radio RF-PECVD method to prepare the DLC thin films. After pre-treating the substrate with hydrogen (H2), we adjusted the methane (CH4) to hydrogen (H2) gas ratio in order to investigate the tribological and optical properties of the DLC film without any additional substrate heating. Then, we used the DLC films as an anti-reflective coating for large scale c-Si solar cells (103 mm 103 mm) under optimum conditions. Thus, in this paper, we investigated the effect of the methane to

Table 1 Deposition conditions Substrates Pre-treatment gas Deposition gas Working pressure RF power Electrode to substrate distance Deposition time Substrate temperature p-type Si(100) corning glass H2: 80 sccm CH4: 1030 sccm H2: 80 sccm 1 Torr 150 W 7 cm 4 min Room temperature

Corresponding author. Tel.: +82 31 290 7141; fax: +82 31 290 7179. E-mail address: byhong@skku.edu (B. Hong). 0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2007.06.019

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reduce their reflectivity. The n+ emitter was formed by conventional phosphorous diffusion using a POCl3 source. The DLC films were deposited by the 13.56 MHz RF-PECVD method. The silver (Ag) and silveraluminum contacts (Ag/Al) on the front (F) and back (B) surfaces of the cells, respectively, were made by screen-printing followed by sintering at 650 750 C for a few minutes. For the sintering process, the screen printed wafers were placed vertically in a fused silica boat in the FFBBFFBB configuration. This boat was then placed in the hot zone of the sintering furnace for a few minutes in order to carry out the sintering in zero air or equivalent N2/O2 ambient. Current voltage (IV) characteristics of the cells were measured at 25 C under simulated AM 1.5 conditions at an intensity of 100 mW/ cm2. The manufacturing process was summarized in Fig. 1.
3. Results and discussion Fig. 2 shows the average value of the hardness of the DLC thin films as a function of the methane flow rate. The hardness of the DLC films increased from 14.5 to 16.2 GPa with increasing methane flow rate. The physical properties of the DLC films are known to depend, to a large degree, on the concentration of carbon atoms in sp2 and sp3 electron configurations and on the extent of film hydrogenation, as well as on the size of clusters of carbon atoms in sp2 configuration [10]. The hardness increases with the increase in the methane flow rate. These results indicate that increasing the methane to hydrogen ratio reduces the hydrogen content and increases the carbon content, thereby making the DLC film harder. In the process of making the solar cell, we fired the cell at 800 C for the purpose of making the electrode. Therefore, we conducted an RTA experiment with our DLC AR coating at 800 C. Fig. 3 shows the SEM images of the DLC thin films after the annealing treatment. In the case where methane flux volumes of 25 and 30 sccm were used (Fig. 3(c) and (d), respectively) they were distorted and delaminated after RTA treatment. This resulted from the fact that the film had poor adhesion and became more highly stressed at a higher methane flow rate. The Raman spectra of the DLC thin films deposited using methane to hydrogen flow ratios ranging from 20 to 80 are shown in Fig. 4. Raman data is widely used for the characterization of the structure of DLC films, due to its ability to distinguish between the sp3 and sp2 bonding types

Fig. 1. Schematics of the manufacturing process of DLC AR coated solar cell.

hydrogen ratio on the tribological and optical properties of the DLC anti-reflective coating and compared the efficiencies of the solar cells with and without this coating. 2. Experiments The DLC films were deposited on the p-type (100) silicon substrates and corning glasses using the 13.56 MHz RF-PECVD method. The substrates were first cleaned using the usual RCA method, followed by in-situ H2 plasma pre-treatment for 10 min at a gas pressure of 133 Pa (1 Torr) and an RF power of 150 W, in order to remove any contaminants on the surface and to activate the surface. Then, methane and hydrogen gases were introduced into the reaction chamber in order to grow the film at room temperature. The substrate was heated only by the plasma during the growth of the film and the deposition time was kept to 4 min for each sample. The samples were deposited at various methane flow rates ranging from 10 to 30 sccm. We varied the methane to hydrogen ratio in order to investigate its effect on the mechanical and optical properties of the DLC film. The experimental parameters are shown in Table 1. The thickness of the DLC thin films was analyzed with a surface profiler (Tencor Alpha-Step 500). To characterize the structure of the DLC films, Raman spectrometry (Jobin-Yvon T64000) was used at a single wavelength of 600 nm, and a nanoindenter (Nano-indenter II, MTS) was used to obtain the hardness of the DLC films. The optical properties of the DLC films were examined using an ultravioletvisible (UVvisible) spectrometer and a spectroscopic ellipsometer (MF-1000, Nano-View). A batch of 20 cells with dimensions of 103 103 cm2 was processed using (100) oriented CZ grown p-silicon wafers having a pseudo square shape (area = 104 cm2) and a resistivity of 1.2 cm. Prior to the diffusion process, the wafers were textured to

Fig. 2. Hardness of the DLC thin films as a function of methane flow rate.

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Fig. 3. SEM images of the DLC thin films as a function of methane flow rate. (a) 15 sccm, (b) 20 sccm, (c) 25 sccm and (d) 30 sccm.

[11]. The Raman spectra were deconvoluted into two Gaussian peaks. The main spectral feature was typical of DLC films, with D and G bands being observed at 1360 and 1560 cm 1, respectively. Fig. 5 shows the optical bandgap of the DLC thin films as a function of the methane flow rate. The Tauc optical bandgap, ETauc, and the E04 bandgap (energy at absorption coefficient = 104 cm 1) decreased as the methane flow rate increased. It is known that the optical gap is influenced by the hybridization state of the carbon atoms. Lowering the content of sp2 bonding in the films widens the optical bandgap, since the carboncarbon sp2 states are located between the carboncarbon

sp3 states [12]. On the other hand, Angus [13] and Dischler et al. [14] reported that the optical bandgap of carbon films could be reduced with decreasing hydrogen content. This result accorded with the nanoindenter result obtained herein, in that increasing the methane to hydrogen ratio reduced the hydrogen content and the optical bandgap. Fig. 6 shows the refractive index (n) measured by the ellipsometer as a function of methane flow rate. The refractive index ranged from 2.06 to 2.22, slightly increasing with increasing methane flow rate. For the application of AR coating to Si device, the refractive index should be around 2 because AR coating is located between air (n = 1) and Si

Fig. 4. Raman spectra of the DLC thin films deposited with a methane to hydrogen ratio of 20 to 80.

Fig. 5. Optical bandgap (Etauc and E04) of the DLC thin films as a function of methane flow rate.

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thickness of 70 nm. It can be seen that the short circuit current slightly increased from 3.07 A to 3.20 A and the efficiency improved from 9.72% to 11.76% due to the presence of the DLC film. This result confirms the possibility of using DLC films as a protective antireflecting coating for silicon solar cells. Fig. 7(b) shows the spectral response Sr() of the cell before and after the DLC AR thin film deposition. The Sr() increased uniformly throughout the spectrum range. The curve shows an increase of Sr() in the 400 nm to 900 nm wavelength region, due to the low reflectance with the DLC film, which increases the generation in the solar cell.

4. Conclusions In this study, we confirmed the possibility of using DLC films as a protective anti-reflecting coating for silicon solar cells. We investigated the effect of the CH4 to H2 ratio on the optical and mechanical properties of the DLC films deposited using the PECVD method. The results of the nano-indenter measurements show that the hardness increases as the methane flow rate increases. The optical bandgap, ETauc, and the E04 bandgap decrease as the methane flow rate increases. The reflectance of the DLC film improved as the methane flow rate increased, with the optimum result being obtained at a methane flow rate of 20 sccm. The refractive index slightly increases as the methane flow rate increases. The currentvoltage characteristic and spectral response of the silicon solar cell showed an improvement after the deposition of the DLC anti-reflection coating. The efficiency of the DLC AR coated solar cell was improved from 9.72% to 11.76%. The fill factor and open-circuit voltage were weakly influenced by the anti-reflection coating. Acknowledgements This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF2005-041-D00314). References
[1] A. Grill, Thin Solid Films 355 (1999) 189. [2] J.-I. Suzuki, S. Okada, Jpn. J. Appl. Phys. 34 (9B) (1995) L1218. [3] M.J. Mirtich, D. Nir, D. Swec, B. Banks, J. Vac. Sci. Technol., A 4 (1986) 2680. [4] T.J. Moravec, J.C. Lee, J. Vac. Sci. Technol. 20 (1982) 338. [5] N. Savvides, J. Appl. Phys. 59 (1986) 4133. [6] Y.F. Lu, S.M. Huang, C.H.A. Huan, X.F. Luo, Appl. Phys., A 68 (1999) 647. [7] M.A. Tamor, C.H. Wu, R.O. Carter, N.E. Lindsay, Appl. Phys. Lett. 55 (1989) 1388. [8] J.-W. Chung, C.-S. Lee, D.-H. Ko, J.H. Han, K.Y. Eun, K.-R. Lee, Diam. Relat. Mater. 10 (2001) 2069. [9] T. Michler, M. Grischke, I. Traus, K. Bewilogua, H. Dimigen, Diam. Relat. Mater. 7 (1998) 459. [10] J. Robertson, Diam. Relat. Mater. 4 (1995) 297. [11] A.A. Ogwu, R.W. Lamberton, S. Morley, P. Maguire, J. McLaughlin, Physica B 269 (1999) 335. [12] K.C. Park, J.H. Moon, J. Jang, Appl. Phys. Lett. 68 (1996) 3594. [13] J.C. Angus, C.C. Hayman, Science 241 (1988) 913. [14] B. Dischler, G. Brandt, P. Koidl, Appl. Phys. Lett. 42 (1983) 636.

Fig. 6. Refractive index (n) of the DLC thin films as a function of methane flow rate.

(n = 3.4). So, all the films' refractive indexes were good for AR coating to Si solar cell. Comparison of IV characteristics was plotted in Fig. 7(a), which shows the forward IV characteristics of a solar cell with an antireflecting (AR) coating, with and without the DLC film, with a

Fig. 7. The characteristics of a solar cell with () and without () an DLC overlayer. (a) IV characteristic and (b) SR characteristic.