煅烧工艺对氧化锌铝(AZO)粉体光学性能的影响

doi:10.3724/SP.J.1077.2013.12185

摘要/Abstract

摘要：

采用聚丙烯酰胺凝胶法制备高浓度Al掺杂ZnO(AZO)前驱体(x(Al)=5.5mol%、6.5mol%), 研究煅烧工艺对AZO粉体光学性能的影响. 结果表明: 随着煅烧温度升高, Al在ZnO中的固溶度降低。当煅烧温度为750℃时, 生成ZnAl₂O₄相。提高煅烧温度, 粉体的紫外吸收峰从366 nm红移至373 nm; 延长煅烧时间, 紫外吸收峰发生蓝移, 吸收强度明显增大。室温下AZO粉体光致发光(PL)光谱主要由354 nm的紫外发射峰、406 nm的近边紫外发射峰和430 nm的蓝光发射峰组成。

关键词: AZO, XPS, UV-Vis吸收性能, 光致发光, 聚丙烯酰胺凝胶法

Abstract:

AZO precursors (x(Al) =5.5mol%, 6.5mol%) were successfully synthesized by the polyacrylamide gel rout. The influence of calcining process on the optical properties of Al-doped-ZnO powders were investigated. It was found that Al concentration in the solution decreased with increasing calcination temperature. The ZnAl₂O₄ phase was detected in the AZO powders after calcined at 750℃. With increasing calcination temperature, the wavelength of UV absorbance peak was moved from 366 nm to 377 nm, while the peak displayed blue shift and the intensity was improved with prolonging calcination time. The room temperature photoluminescence spectra showed that emission peaks were composed of ultraviolet peak (354 nm), detectable ultraviolet peak (406 nm) and blue emission peak (430 nm).

Key words: AZO, XPS, UV-Vis absorbance property, photoluminescence, polyacrylamide gel rout

中图分类号:

TP104

王志勇, 彭超群, 王日初, 王小锋, 刘兵. 煅烧工艺对氧化锌铝(AZO)粉体光学性能的影响[J]. 无机材料学报, 2013, 28(2): 171-176.

WANG Zhi-Yong, PENG Chao-Qun, WANG Ri-Chu, WANG Xiao-Feng, LIU Bing. Influence of Calcining Process on Optical Properties of Al-doped-ZnO Powders[J]. Journal of Inorganic Materials, 2013, 28(2): 171-176.

图/表 10

图1 AZO前驱体(x(Al)=5.5mol%)的DSC曲线

Fig. 1 DSC curve of AZO precusor (x(Al)=5.5mol%)

图2 不同煅烧温度下AZO粉体(x(Al)= 5.5mol%)的XRD图谱

Fig. 2 XRD patterns of AZO powders (x(Al)= 5.5mol%) calcined at different temperatures

图3 在600℃煅烧条件下AZO粉体的XPS能谱全谱

Fig. 3 XPS survey spectrum of the AZO powders (x(Al)=5.5%) calcined at 600℃

图4 在600℃煅烧条件下AZO粉体(x(Al)=5.5mol%)中Al元素的XPS放大谱

Fig. 4 XPS data of Al element in AZO powders (x(Al)=5.5mol%) calcined at 600℃

图5 所示为不同煅烧温度下保温1 h制备的AZO粉体(x(Al)=5.5mol%)的扫描电镜照片。由图5可见, AZO颗粒形貌多样, 尺寸不均匀。Al3+容易分散在比表面积大的小晶粒晶界上, 阻碍小晶粒进一步长大, 而较大尺寸晶粒晶界上分散Al3+浓度小, 对晶粒的生长影响较小, 因此, ZnO颗粒表现出不均匀性[15]。从图5(a)和5(b)可以看出, 当煅烧温度为500℃时, 晶粒尺寸较小, 为20~40 nm, 粉体出现明显团聚; 随着温度升至600℃, 晶粒在一定程度上发生长大, 尺寸为30~50 nm(见图5(c)和(d)); 当煅烧温度升高至750℃时, 晶粒形貌多为球状, 晶粒尺寸增至40~80 nm, 粉体的团聚程度降低(见图5(e)和(f))。

图5 不同煅烧温度制备的AZO粉体(x(Al)=5.5mol%)的SEM照片

Fig. 5 SEM images of AZO powders (x(Al)=5.5mol%) calcined at different temperatures

图6 不同煅烧温度的AZO粉体(x(Al)=5.5mol%)的紫外-可见光吸收光谱

Fig. 6 UV-Vis absorbance spectra of AZO powders (x(Al)=5.5mol%) calcined at different temperatures

图7 不同煅烧时间的AZO粉体(x(Al)=6.5mol%)的紫外-可见光吸收光谱

Fig. 7 UV-Vis absorbance spectra of AZO powders (x(Al)=6.5mol%) calcined at 550℃ for different time

图8 AZO粉体(x(Al)=5.5mol%)的光致发光(PL)图谱

Fig. 8 PL spectra of AZO powders (x(Al)=5.5mol%) calcined at different temperatures

图9 不同煅烧时间AZO粉体(x(Al)=6.5mol%)的光致发光(PL)图谱

Fig. 9 PL spectra of AZO powders (x(Al)=6.5mol%) calcined at 550℃ for different time

参考文献 22

[1]	Wahab Rizawan, Ansari S G, Kim Y S, et al. Low temperature solution synthesis and character- ization of ZnO nano-flowers. Materials Research Bulletin, 2007, 42(9): 1640-1648.
[2]	张霞, 焦宝祥, 孙芳芳. ZnO基荧光粉的制备及荧光光谱分析. 量子电子学报, 2010, 27(6): 661-664.
[3]	李玲, 白建双, 金志探, 等. 掺杂对纳米ZnO粉体紫外-可见光吸收性能的影响. 华南理工大学学报: 自然科学版, 2004, 32(6): 41-44.
[4]	Yu Y S, Kim G Y, Min B H, et al. Optical characteristic of Ge doped ZnO compound. Journal of the European Ceramic Society, 2004, 24(6): 1865-1868.
[5]	Yousefi Ramin, Kamaluddin Burhanuddin. The effects of annealing temperature on structural and optical properties of S-doped ZnO nanobelts. Solid State Science, 2010, 12(2): 252-256.
[6]	He Jr H, Lao Chang S, Chen Lin J, et al. Large-Scale Ni-doped ZnO nanowire arrays and electrical and optical properties. Journal of American Chemical society, 2005, 127(47): 16376-16377.
[7]	Qu Xiu-rong, Lv Shu-chen, Bai Li-na, et al. Electronic structure and optical properties of Sn-doped ZnO. Physica B: Condensed Matter, 2012, 407(2): 268-270.
[8]	Rajeswari Yougamalar N, Chandra Bose A. Absorption-emission study of hydrotherapy grown Al:ZnO nanostructures. Journal of Alloys and Compounds, 2011, 509(34): 8493-8500.
[9]	Liang Yuan-chang. Microstructure and optical properties of electrodeposited Al-doped ZnO nanosheets. Ceramics International, 2012, 38(1):119-124.
[10]	Zhang Yu-long, Yang Ye, Zhao Jun-hua, et al. Optical and electrical properties of aluminum doped zinc oxide nanoparticles. Journal of Material Society, 2011, 46(3): 774-780.
[11]	Wang Xiao-feng, Wang Ri-chu, Peng Chao-qun, et al. Growth of BeO nanograins sythesized by polycrylamide gel route. Journal of the Material Society Technology, 2011, 27(2):147-152.
[12]	Wu Song-quan, Liu Yu-yan, He Li-na, et al. Preparation of β-Sphodumenne-Based glass-ceramic powder by polyacrylamine gel process. Materials Letters, 2004, 58(22/23): 2772-2775.
[13]	Kunar K, Ramamoorthy K, Koinkar P M, et al. A novel way of modifying nano grain size by solution concentration in the growth of ZnAl2O4 thin films. Journal of Nanoparticle Research, 2007, 9(2): 331-335.
[14]	Wang Xing-ming, Bai Xue, Duan Hua-ying, et al. Preparation of Al-doped ZnO sputter target by hot pressing. Transactions of Nonferrous Metals Society of China, 2011, 21(7): 1550-1556.
[15]	Serier H, Demourgues A, Majimel J, et al. Infrared absorptive properties of Al-doped ZnO divided powder. Journal of Solid State Chemistry, 2011, 184(6): 1523-1529.
[16]	Rajeswari Yougamalar N, Chandra Bose A. Burstein-Moss shift and room temperature near bandedge luminescence in lithium-doped zinc oxide. Applied Physics A, 2011, 103(1): 33-42.
[17]	陈航, 邓宏, 戴丽萍, 等. 掺Cd对ZnO薄膜光学性能的影响. 人工晶体学报, 2008, 37(1): 213-217.
[18]	Davide Cozzoli P, Lucia Curri, Angela Agostiano A. ZnO nanocrystals by non-hydrolytic rout: synthesis and characterization. Journal of Physical Chemical B, 107(20): 4756-4762.
[19]	Piticescu Robert R, Piticescu Roxana M, Monty Claude J. Synthsis of Al-doped ZnO nanomaterials with controlled luminescence. Journal of the European Ceramic Society, 2006(26): 2979-2983.
[20]	Zeng Hai-bo, Duan Guo-tao, Li Yue, et al. Blue luminescence of ZnO nanoparticles based on non-equilibrium processes: defect origins and emission controls. Advance Function Materials, 2010, 20(4): 561-572.
[21]	Bai S N, Tsai H H, Tseng T Y. Structural and optical properties of Al-doped ZnO nanowires synthesized by hydrothermal method. Thin Solid Films, 2007, 516(2/4): 155-158.
[22]	Chen K J, Fang T H, Huang F Y, et al.The crystallization and physical properties of Al-doped ZnO nanoparticles. Applied Surface Science, 254(18): 5791-5795.