铟掺杂调控氧化锌纳米棒长径比

doi:10.3866/PKU.WHXB201504221

摘要/Abstract

摘要：

利用水热法合成了铟掺杂的氧化锌(In-ZnO)纳米棒. X射线衍射(XRD)结果表明铟掺杂能导致氧化锌晶格膨胀. 扫描电镜(SEM)结果显示, 随着前驱液中铟浓度的增加, 氧化锌纳米棒的长径比先减小后增大, 在铟原子浓度为1.0% (原子分数, x), 长径比达到最小值; 随着前驱液中铟浓度继续增加, 长径比增大. 从晶体生长角度考虑, 溶液中存在四羟基铟(In(OH)₄^-)生长基元, 该生长基元可转化为铟替位掺杂(In_Zn)和羟基铟氧化物(InOOH)两种状态, 二者之间存在竞争关系, 共同引起长径比的非线性变化. 当铟原子分数小于1.0%时, In_Zn是主要存在形式, 其能破坏锌极性面, 从而抑制(002)晶面的生长. 当铟原子浓度高于1.0%时, 生成微量的InOOH, 其能起到晶粒粘结剂的作用, 促进(002)面的生长. 因此, 可以通过改变前驱液中铟的浓度, 调控氧化锌纳米棒的长径比. 本文阐述了In-ZnO的生长机理, 并提供一种制备实用的掺杂氧化锌纳米棒的方法.

关键词: ZnO, In掺杂, 水热法, 长径比, 生长模型

Abstract:

In-doped ZnO nanorods (NRs) were synthesized by hydrothermal method. The X-ray diffraction (XRD) patterns showed that the ZnO lattices expanded upon In doping. According to the scanning electron microscopy (SEM) images, the aspect ratio (length- to- width ratio) of the ZnO NRs decreased as the concentration of In(III) in the precursor solution increased from 0% to 1.0% (atomic fraction, x), and increased with further increases in the In(III) concentration from 1.0%to 5.0%. The nonlinear modulation of the aspect ratio of ZnO NRs is believed to be due to the competition between the subst itutional doping of In³⁺ (In_Zn) and formation of InOOH intermediate, both of which are closely related to the behavior of In(OH)₄^-. In(OH)₄^- can be adsorbed onto zinc polar plane, and thus inhibits adsorption of Zn(OH)₄^2- growth units. Furthermore, In(OH)₄^- can convert into InOOH, which can act as a crystal binder and enhance growth along the (002) plane. In_Zn can disrupt the zinc polar plane, resulting in the suppression of growth along the (002) facet. Therefore, the aspect ratio of ZnO NRs can be controllably modulated by changing the In concentration in the precursor solution. The current study furthers our understanding of the growth mechanism of In-doped ZnO, and presents a feasible method to prepare doped-ZnO NRs for real applications.

Key words: ZnO, In-doping, Hydrothermal method, Aspect ratio, Growth model

胡海峰, 贺涛. 铟掺杂调控氧化锌纳米棒长径比[J]. 物理化学学报, 2015, 31(7), 1421-1429. doi: 10.3866/PKU.WHXB201504221

HU Hai-Feng, HE Tao. Controlled Aspect Ratio Modulation of ZnO Nanorods via Indium Doping[J]. Acta Phys. -Chim. Sin. 2015, 31(7), 1421-1429. doi: 10.3866/PKU.WHXB201504221

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201504221

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I7/1421

参考文献

(1) Tam, K. H.; Cheung, C. K.; Leung, Y. H.; Djuriši?, A. B.; Ling, C. C.; Beling, C. D.; Fung, S.; Kwok, W. M.; Chan, W. K.; Phillips, D. L.; Ding, L.; Ge, W. K. J. Phys. Chem. B 2006, 110, 20865. doi: 10.1021/jp063239w
(2) Zhu, H. L.; Yang, D. R.; Zhang, H. Inorg. Mater. 2006, 42 (11), 1210. doi: 10.1134/S0020168506110070
(3) Kong, X. Y.; Ding, Y.; Yang, R. S.; Wang, Z. L. Science 2004, 303, 1348. doi: 10.1126/science.1092356
(4) Yen, K. Y.; Chiu, C. H.; Hsiao, C. Y.; Li, C.W.; Chou, C. H.; Lo, K. Y.; Chen, T. P.; Lin, C. H.; Lin, T. Y.; Gong, J. R. J. Crystal Growth 2014, 387, 91. doi: 10.1016/j.jcrysgro.2013.10.042
(5) Bae, S. Y.; Na, C.W.; Kang, J. H.; Park, J. J. Phys. Chem. B 2005, 109, 2526. doi: 10.1021/jp0458708
(6) Xu, L.; Su, Y.; Chen, Y. Q.; Xiao, H. H.; Zhu, L.; Zhou, Q. T.; Li, S. J. Phys. Chem. B 2006, 110, 6637. doi: 10.1021/jp057476v
(7) Wang, B. Q.; Xia, C. H.; Fu, Q.; Wang, P.W.; Shan, X. D.; Yu, D. P. Acta Phys. -Chim. Sin. 2008, 24 (7), 1165. [王百齐, 夏春辉, 富强, 王朋伟, 单旭东, 俞大鹏. 物理化学学报, 2008, 24 (7), 1165.] doi: 10.3866/PKU.WHXB20080708
(8) Chen, H. S.; Qi, J. J.; Huang, Y. H.; Liao, Q. L.; Zhang, Y. Acta Phys. -Chim. Sin. 2007, 23 (1), 55. [陈红升, 齐俊杰, 黄运华, 廖庆亮, 张跃. 物理化学学报, 2007, 23 (1), 55.] doi: 10.1016/S1872-1508(07)60005-9
(9) Wang, J.; Zhuang, H. Z.; Xue, C. S.; Li, J. L.; Xu, P. Acta Phys. -Chim. Sin. 2010, 26 (10), 2840. [王杰, 庄惠照, 薛成山, 李俊林, 徐鹏. 物理化学学报, 2010, 26 (10), 2840.] doi: 10.3866/PKU.WHXB20101024
(10) Ghosh, S.; Saha, M.; De, S. K. Nanoscale 2014, 6, 7039. doi: 10.1039/c3nr05608b
(11) Su, J.; Li, H. F.; Huang, Y. H.; Xing, X. J.; Zhao, J.; Zhang, Y. Nanoscale 2011, 3, 2182. doi: 10.1039/c1nr10018a
(12) Ismardi, A.; Tiong, T. Y.; Dee, C. F.; Majlis, B. Y. AIP Conf. Proc. 2011, 1341, 25.
(13) Kumar, G. M.; Park, J. J. Colloid Interface Sci. 2014, 430, 229. doi: 10.1016/j.jcis.2014.05.045
(14) Pradhan, D.; Leung, K. T. Langmuir 2008, 24, 9707. doi: 10.1021/la8008943
(15) Xia, Y. J.; Guan, Z. S.; He, T. Chin. Phys. B 2014, 23 (8), 087701-1. [夏玉静, 管自生, 贺涛. 中国物理B, 2014, 23 (8), 087701-1.] doi: 10.1088/1674-1056/23/8/087701
(16) Yang, F.; Liu, W. H.; Wang, X.W.; Zheng, J.; Shi, R. Y.; Zhao, H.; Yang, H. Q. ACS Appl. Mater. Interfaces 2012, 4, 3852. doi: 10.1021/am300561w
(17) Bae, S. Y.; Choi, H. C.; Na, C.W.; Park, J. App. Phys. Lett. 2005, 86, 033102. doi: 10.1063/1.1851591
(18) Ahmad, M.; Sun, H.; Zhu, J. ACS Appl. Mater. Interfaces 2011, 3, 1299. doi: 10.1021/am200099c
(19) Height, M. J.; Mädler, L.; Pratsinis, S. E. Chem. Mater. 2006, 18 (2), 572. doi: 10.1021/cm052163y
(20) Fu, Z. P.; Yang, B. F.; Li, L.; Dong, W.W.; Jia, C.; Wu, W. J. Phys.: Condes. Matter 2003, 15, 2867. doi: 10.1088/0953-8984/15/17/335
(21) Mahmood, K.; Park, S. B.; Sung, H. J. J. Mater. Chem. C 2013, 1, 3138. doi: 10.1039/c3tc00082f
(22) Wanger, C. D.; Riggs, W. M.; Davis, L. E.; Moulder, J. F.; Muilenberg, G. E. Handbook of X-Ray Photoelectron Spectroscopy; Perkin-Elmer Corp.: Eden Prairie, 1979; pp 1-190.
(23) Faur, M.; Faur, M.; Jayne, D. T.; Goradia, M.; Goradia, C. Surface and Interface Analysis 1990, 15, 641.
(24) Kazmerski, L. L.; Jamjoum, O.; Ireland, P. J.; Deb, S. K.; Mickelsen, R. A.; Chen, W. J. Vac. Sci. Technol. 1981, 19, 467. doi: 10.1116/1.571040
(25) Lin, A.W. C.; Armstrong, N. R.; Kuwana, T. Anal. Chem. 1977, 49 (8), 1228. doi: 10.1021/ac50016a042
(26) McGuire, G. E.; Schweitzer, G. K.; Carlson, T. A. Inorg. Chem. 1973, 12, 2450. doi: 10.1021/ic50128a045
(27) Nefedov, V. I.; Gati, D.; Dzhurinskii, B. F.; Sergushin, N. P.; Salyn, Y. V. Zh. Neorg. Khimii 1975, 20, 2307.
(28) Cahen, D.; Ireland, P. J.; Kazmerski, L. L.; Thiel, F. A. J. Appl. Phys. 1985, 57, 4761. doi: 10.1063/1.335341
(29) Bertrand, P. A. J. Vac. Sci. Technol. 1981, 18, 28. doi: 10.1116/1.570694
(30) Clark, D. T.; Fok, T. Thin Solid Films 1980, 70 (2), 261. doi: 10.1016/0040-6090(80)90367-3
(31) Fan, J. C. C.; Goodenough, J. B. J. Appl. Phys. 1977, 48, 3524. doi: 10.1063/1.324149
(32) Hewitt, R.W.; Winograd, N. J. Appl. Phys. 1980, 51, 2620. doi: 10.1063/1.327991
(33) Wang, X. H.; Sun, L. X. One Process of Orthorhombic InOOH Synthesized by Microemulsion-Solvothermal Method. CN 103241767 A, 2013-08-14. [王晓华, 孙兰轩. 一种斜方晶 InOOH 的微乳-溶剂热工艺: 中国, CN 103241767 A [P]. 2013- 08-14.]
(34) Liu, Q. S.; Lu, W. G.; Ma, A. H.; Tang, J. K.; Lin, J.; Fang, J. Y. J. Am. Chem. Soc. 2005, 127, 5276. doi: 10.1021/ja042550t
(35) Ahmad, M.; Zhao, J.; Iqbal, J.; Miao, W.; Xie, L.; Mo, R. G.; Zhu, J. J. Phys. D: Appl. Phys. 2009, 42, 165406. doi: 10.1088/0022-3727/42/16/165406
(36) Govender, K.; Boyle, D. S.; Kenway, P. B.; O'Brien, P. J. Mater. Chem. 2004, 14, 2575. doi: 10.1039/b404784b
(37) Wood, S. A.; Samson, I. M. Ore Geol. Rev. 2006, 28, 57. doi: 10.1016/j.oregeorev.2003.06.002
(38) Wang, B. G.; Callahan, M. J.; Xu, C. C.; Bouthillette, L. O.; Giles, N. C.; Bliss, D. F. J. Cryst. Growth 2007, 304, 73. doi: 10.1016/j.jcrysgro.2007.01.047
(39) Morales, A. E.; Zaldivar, M. H.; Pal, U. Opt. Mater. 2006, 29, 100. doi: 10.1016/j.optmat.2006.03.010
(40) Wang, B. The Preparation of In2O3 Nanomaterials with Different Phase Structures and Their Gas Sensing Properties. M. S. Dissertation, Beijing University of Chemical Technology, Beijing, 2011. [王彬. 不同晶型氧化铟纳米材料的制备及其气敏性能研究[D]. 北京: 北京化工大学, 2011.]
(41) Zhuang, Z. B.; Peng, Q.; Liu, J. F.; Wang, X.; Li, Y. D. Inorg. Chem. 2007, 46, 5179. doi: 10.1021/ic061999f
(42) Xu, X. X.; Wang, X. Inorg. Chem. 2009, 48, 3890. doi: 10.1021/ic802449w
(43) Chen, C. L.; Chen, D. R.; Jiao, X. L.; Wang, C. Q. Chem. Commun. 2006, 4632.
(44) Li, Z. H.; Xie, Z. P.; Zhang, Y. F.; Wu, L.; Wang, X. X.; Fu, X. Z. J. Phys. Chem. C 2007, 111, 18348. doi: 10.1021/jp076107r
(45) Yu, D. B.; Yu, S. H.; Zhang, S. Y.; Zuo, J.; Wang, D. B.; Qian, Y. T. Adv. Funct. Mater. 2003, 13, 497. doi: 10.1002/adfm.200304303
(46) Hafeez, M.; Zhai, T. Y.; Bhatti, A. S.; Bando, Y.; Golberg, D. Cryst. Growth Des. 2012, 12, 4935. doi: 10.1021/cg300870y
(47) Pacholski, C.; Kornowski, A.; Weller, H. Angew. Chem. Int. Edit. 2002, 41, 1188.
(48) Sangwal, K. J. Cryst. Growth 1998, 192, 200. doi: 10.1016/S0022-0248(98)00424-2
(49) Yang, H. X. Solvothermal Synthesis of In2O3 and CeO2 Nanostructures: Structural Studies and Application. Ph. D. Dissertation, Shandong University, Jinan, 2013. [杨红晓. 溶剂热法合成氧化铟、氧化铈纳米结构及其性能研究[D]. 济南: 山东大学, 2013.]

[1]	孔菁, 张金贵, 张素芬, 奚菊群, 沈明. 可见光激发的BiOI/ZnO纳米复合抗菌剂制备及其抗菌活性与机制[J]. 物理化学学报, 2023, 39(12): 2212039 - .
[2]	韩高伟, 徐飞燕, 程蓓, 李佑稷, 余家国, 张留洋. 反蛋白石结构ZnO@PDA用于增强光催化产H₂O₂性能[J]. 物理化学学报, 2022, 38(7): 2112037 - .
[3]	刘影, 刘晓放, 夏林, 黄超杰, 吴兆萱, 王慧, 孙予罕. 以类水滑石为前驱体的Cu/ZnO/Al₂O₃催化剂用于CO_x加氢合成甲醇：CO在反应混合物中的作用[J]. 物理化学学报, 2022, 38(3): 2002017 - .
[4]	李聪明, 陈阔, 王晓月, 薛楠, 杨恒权. 探究Cu/ZnO相互作用对CO₂加氢制甲醇反应性能的影响[J]. 物理化学学报, 2021, 37(5): 2009101 - .
[5]	杨世杰, 徐向群, 程新兵, 王鑫萌, 陈金秀, 肖也, 袁洪, 刘鹤, 陈爱兵, 朱万诚, 黄佳琦, 张强. 柱状金属锂沉积物：电解液添加剂的影响[J]. 物理化学学报, 2021, 37(1): 2007058 - .
[6]	吕翰林, 胡兵, 刘国亮, 洪昕林, 庄林. ZnO逆修饰小尺寸Cu/SiO₂催化剂及其在CO₂加氢制甲醇中的应用[J]. 物理化学学报, 2020, 36(11): 1911008 - .
[7]	冯英杰, 王进平, 刘丽丽, 王习东. ZnO纳米棒阵列到纳米管结构的自转化机制及其在相变封装材料中的应用[J]. 物理化学学报, 2019, 35(6): 644 -650 .
[8]	尹雅芝,胡兵,刘国亮,周晓海,洪昕林. 利用ZnO@ZIF-8核壳结构构建高选择性、高稳定性的Pd/ZnO催化剂用于CO₂加氢制甲醇[J]. 物理化学学报, 2019, 35(3): 327 -336 .
[9]	黄志娟,喻志农,李言,王吉政. 石墨炔修饰的ZnO薄膜紫外探测器[J]. 物理化学学报, 2018, 34(9): 1088 -1094 .
[10]	赵新飞,陈浩,吴昊,王睿,崔义,傅强,杨帆,包信和. 氧化锌有序结构在Au(111)和Cu(111)上的生长[J]. 物理化学学报, 2018, 34(12): 1373 -1380 .
[11]	刘强,韩永,曹云君,李小宝,黄武根,余毅,杨帆,包信和,李毅敏,刘志. 利用原位APXPS与STM研究H₂在ZnO(10${\rm{\bar 1}}$0)表面的活化[J]. 物理化学学报, 2018, 34(12): 1366 -1372 .
[12]	许利刚, 邱伟, 陈润锋, 张宏梅, 黄维. ZnO电极修饰层在钙钛矿太阳能电池中的应用[J]. 物理化学学报, 2018, 34(1): 36 -48 .
[13]	陈凡,王中跃,张艳艳,余柯涵,翁丽星,韦玮. 聚丙烯酸功能化高效发光的La_1-xEu_xF₃纳米晶合成及细胞成像[J]. 物理化学学报, 2017, 33(7): 1446 -1452 .
[14]	张云龙,章俞之,宋力昕,郭云峰,吴岭南,张涛. 砚状ZnO/石墨烯复合物的制备及其光催化性能[J]. 物理化学学报, 2017, 33(11): 2284 -2292 .
[15]	张晓茹,许跃峰,沈守宇,陈媛,黄令,李君涛,孙世刚. 锂氧电池双功能还原石墨烯-LaFeO₃复合纳米催化剂的制备及性能[J]. 物理化学学报, 2017, 33(11): 2237 -2244 .