电子显微学报 Journal of Chinese Electron Microscopy Society Vol. 33 No XPS AFM 廖荣 1,2, 张海燕 1*, 王道然 2, 杨铁铮 2

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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.

1 电子显微学报 Journal of Chinese Electron Microscopy Society Vol. 33 No 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 ; 2. 华南理工大学电子与信息学院, 广东广州 ) 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; TG A doi /j 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 CIG CIGS JGP-560B ALD-ZnO ZnO XPS X CuGa AFM % In 8 Fig. 1 Schematic cross section of CIGS solar cell structure % CIG No. x2dx-y No liaorong@ scut. edu. cn * hyzhang@ gdut. edu. cn

216 J. Chin. Electr. Microsc. Soc. 33 3 10-4 Pa 1. 2 99. 999% 1.

2 216 J. Chin. Electr. Microsc. Soc Pa % 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 min min 3 A3 In 10 min 2. 1 CIGS AFM CuGa 30 min In 10 min min min μm 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 ms B1 B2 B3 3 s μm ~ 2. 0 μm hpa 400 CIGS 30 nm ~ 60 nm ZnO 50 nm Axis Ultra DLD 100 mw /cm 2 30 min min 2 A2 AM 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 3 XPS AFM CIGS XPS XPS In XPS In 3d5 /2 3d3 /2 3 A3 XPS ev ev In + 3 4c Se XPS Se 3d ev C1s ev ev Se CIGS shirley-type - 2 4d Ga Lorentzian-Gaussian 3 CIGS Cu In Ga Se O C Na ev Cu I CIGS Cu + 1 4b Ga Ga Ga 3d Ga + 3 XPS O XPS 4a Cu XPS 1 CIGS Cu2p3 / ev CuIn 0. 7 Ga 0. 3 Se 2 Cu2p1 / ev Peak Position BE ev Table 1 FWHM ev Fig CIGS XPS XPS full spectrum of CIGS thin film. CIGS XPS XPS quantification report of CIGS thin films Raw Area CPS RSF Cu 2p In 3d Se 3d Ga 3d ALD-ZnO ZnO DEZn ms ZnO AFM 3 μm 3 μm 150 ms nm DEZn 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.

4 218 J. Chin. Electr. Microsc. Soc 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

5 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 ev O 1s ZnO ev C O C COOH 7b O1s Zn O O C O C Position Peak BE ev Fig. 7 Fig 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 C 1s Zn 2p 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.

6 220 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 AM V oc = 0. 46V J sc = 13. 8mA / cm 2 2. CIGS 9 Fig. 9 FF = η 3. 84% 3 CIGS ZnO D CIGS D J. B CIGS J J D D J Photographs of a Cd-free CIGS solar cell. 10. CIGS D

7 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 School of Electronic and Information Engineering South China University of Technology Guangzhou Guangdong 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

s 15 contact s W Si 3 N μm N / m 4 AFM 95% AFM WPOJ UPOJ WPOJ UPOJ 260 ~ 280 nm WPOJ-DS UPOJ-DS 1 cm 1 cm DEAE-ce

s 15 contact s W Si 3 N μm N / m 4 AFM 95% AFM WPOJ UPOJ WPOJ UPOJ 260 ~ 280 nm WPOJ-DS UPOJ-DS 1 cm 1 cm DEAE-ce 32 1 2013 2 Journal of Chinese Electron Microscopy Society Vol. 32 No. 1 2013-02 1000-6281 2013 01-0054-08 1 1* 2 1 1 1. 2. 710062 AFM SEM WPOJ-DS UPOJ-DS WPOJ-DS β- UPOJ-DS AFM WPOJ-DS UPOJ-DS SEM UPOJ-DS