33 3 2014 6 电子显微学报 Journal of Chinese Electron Microscopy Society Vol. 33 No. 3 2014-06 1000-6281 2014 03-0215-07 XPS AFM 廖荣 1,2, 张海燕 1*, 王道然 2, 杨铁铮 2 2, 范宇 ( 1. 广东工业大学材料与能源学院, 广东广州 510006; 2. 华南理工大学电子与信息学院, 广东广州 510640) 应用溅射后硒化法和原子层沉积法分别制备了无镉的铜铟镓硒电池关键膜层 CIGS 光吸收薄膜和 ZnO 缓 冲层, 着重对该两膜层进行 XPS 和 AFM 表面分析, 得到比较理想的制备工艺条件, 并结合其它检测方法 : SEM XRD 及吸收光谱等, 证明采用操作简便 成本低廉的该工艺能制备出无镉的铜铟镓硒电池通过 I-V 测试结果, 该 电池有一定的光电转换效率 原子层沉积 ; 氧化锌 ; XPS; AFM; 无镉的铜铟镓硒太阳能电池 TM615; TG115. 21 + 5. 7 A doi 10. 3969 /j. 1000-6281. 2014. 03. 004 CdS Cu In 1 - x Ga x Se 2 CIGS CIGS 1 CdS 2 1 CBD CdS 2 3 CdS 2. 4 ~ 2. 5 ev 3 CdS 1 1 ALD-ZnO CdS CIGS /ZnO pn 4 ALD 5 ALD- ZnO CdS CIGS 6 CIGS 1. 1 7 CIG CIGS JGP-560B ALD-ZnO ZnO XPS X CuGa AFM 3 1 99. 999% In 8 Fig. 1 Schematic cross section of CIGS solar cell structure. 1 99. 999% CIG 2014-03 - 05 2014-04 - 03 2013 No. x2dx-y1130010 No. 201210561042. 1970 -. E-mail liaorong@ scut. edu. cn * 1958 -. E-mail hyzhang@ gdut. edu. cn
216 J. Chin. Electr. Microsc. Soc. 33 3 10-4 Pa 1. 2 99. 999% 1. 3 Pa CuGa 70 W In 70W CIG CSPM4000 X - XPS 9 A1 A2 A3 1 A1 In 20 min CuGa CuGa 15 min In 20 min CuGa 15 min 200 20 min 560 30 min 3 A3 In 10 min 2. 1 CIGS AFM CuGa 30 min In 10 min 250 20 min 560 30 min 23. 953 μm 23. 953 μm Picosun Oy R - 75 A1 ALD ZnO ALD-ZnO Zn C 2 H 5 2 DEZn DI-water A2 640 nm 120 A3 H 2 O 0. 1 s 4 s 1. 1 N 2 DEZn 150 sccm μm 41 nm CIGS H 2 O 200 sccm 250 DEZn 100 150 200 ms B1 B2 B3 3 s 20 1. 0 μm ~ 2. 0 μm hpa 400 CIGS 30 nm ~ 60 nm ZnO 50 nm Axis Ultra DLD 100 mw /cm 2 30 min 560 30 min 2 A2 AM1. 5 2 2 A1 A2 A3 CIGS AFM 2 μm 1. 0 μm 174 nm A3 A3 XPS 2 CIGS AFM A1 A2 A3 3 Fig. 2 AFM image of CIGS thin film.
3 XPS AFM 217 2. 2 CIGS XPS XPS In XPS In 3d5 /2 3d3 /2 3 A3 XPS 443. 3 ev 451. 1 ev In + 3 4c Se XPS Se 3d 53. 5 ev 57 3. 5 C1s 284. 6 ev ev Se CIGS shirley-type - 2 4d Ga Lorentzian-Gaussian 3 CIGS Cu In Ga Se O C Na 19. 8 ev Cu I 19. 9 CIGS Cu + 1 4b Ga Ga Ga 3d Ga + 3 XPS O XPS 4a Cu XPS 1 CIGS Cu2p3 /2 932. 65 ev CuIn 0. 7 Ga 0. 3 Se 2 Cu2p1 /2 952. 45 ev Peak Position BE ev Table 1 FWHM ev Fig. 3 1 3 CIGS XPS XPS full spectrum of CIGS thin film. CIGS XPS XPS quantification report of CIGS thin films Raw Area CPS RSF Cu 2p 932. 000 3. 646 75 650. 0 5. 321 63. 549 25. 58 20. 78 In 3d 442. 000 2. 742 66 213. 3 7. 265 114. 820 20. 40 12. 01 Se 3d 52. 000 2. 844 7 726. 7 0. 853 78. 982 45. 44 65. 15 Ga 3d 15. 000 3. 121 10 556. 7 0. 439 69. 725 8. 98 2. 05 2. 3 ALD-ZnO ZnO DEZn 5 3 100 ms ZnO AFM 3 μm 3 μm 150 ms 1. 45 nm DEZn 100 150 200 ms
218 J. Chin. Electr. Microsc. Soc. 33 4 CIGS XPS a Cu b In c Se d Ga Fig. 4 XPS diagram of CIGS thin films. a Cu high resolution spectrum b In high resolution spectrum c Se high resolution spectrum d Ga high resolution spectrum Fig. 5 5 ZnO AFM a T = 100 ms b T = 150 ms c T = 200 ms AFM images of ZnO films with different zinc sources time. a T = 100 ms b T = 150 ms c T = 200 ms ALD
3 XPS AFM 219 B1 100 ms 7a C1s C CH x B1 XPS 2. 4 ALD-ZnO XPS 6 B1 XPS Zn 2p3 /2 2 ALD-ZnO XPS 8 2 1 021. 5 ev O 1s 530. 5 ZnO ev C O C COOH 7b O1s Zn O O C O C Position Peak BE ev Fig. 7 Fig. 6 7 6 ALD-ZnO XPS XPS full spectrum of ALD-ZnO thin film. ZnO C1s O1s C1s and O1s high resolution spectrum of ZnO thin films. 2 ALD-ZnO XPS Table 2 XPS quantification report of ALD-ZnO thin films FWHM Raw Area RSF ev CPS O 1s 527. 100 1. 308 75 792. 0 0. 780 15. 999 31. 57 20. 11 C 1s 281. 900 1. 128 33 696. 7 0. 278 12. 011 46. 23 22. 11 Zn 2p 1 018. 350 1. 558 479 639. 6 5. 589 65. 387 22. 20 57. 78 2. 5 Mo SEM XRD TEM Cu In Ga CIGS 4 9 ZnO ZnO ZnO
220 J. Chin. Electr. Microsc. Soc. 33 Fig. 8 8 ZnO Zn 2p Zn 2p high resolution spectrum of ZnO thin film. Al Ag 10 9 A3 B1 1. CIGS I-V 100 mw/ J. cm 2 AM1. 5 2012 32 9 834-840. V oc = 0. 46V J sc = 13. 8mA / cm 2 2. CIGS 9 Fig. 9 FF = 0. 59 η 3. 84% 3 CIGS ZnO D. 2011. 3. CIGS D. 2012. 4. J. B 2013 27 6 27-32. 5. CIGS J. 2012 32 4 347-351. 6. J. 2006 35 11 957-960. 7. D. 2011. 8. D. 2009. 9. J. 2013 33 5 496-500. Photographs of a Cd-free CIGS solar cell. 10. CIGS D. 2013.
3 XPS AFM 221 XPS and AFM analysis of key layer of Cd-free CIGS solar cell LIAO Rong 1 2 ZHANG Hai-yan 1* WANG Dao-ran 2 YANG Tie-zheng 2 FAN Yu 2 1. School of Material and Energy Guangdong University of Technology Guangzhou Guangdong 510006 2. School of Electronic and Information Engineering South China University of Technology Guangzhou Guangdong 510641 China Abstract CuIn 1 - x Ga x Se 2 light absorbing film and ZnO buffer layer for Cd-free CIGS solar cell were prepared by evaporating selenylation method after sputtering and atomic layer deposition. The two films were analyzed by X-ray photoelectron spectroscopy atomic force microscope scanning electron microscope X-ray diffraction and absorption spectrum. The optimized preparation conditions were obtained. A photoelectric conversion efficiency of 3. 84% was obtained in the Cd-free CIGS solar cell from the low-cost and simple preparation method. Keywords atomic layer deposition zinc oxide XPS AFM Cd-free CIGS solar cell * Corresponding author