锰掺杂诱导正交相SnO2 的生长行为

doi:10.3969/j.issn.1007-2861.2013.05.004

上海大学学报(自然科学版) ›› 2013, Vol. 13 ›› Issue (5): 459-464.doi: 10.3969/j.issn.1007-2861.2013.05.004

锰掺杂诱导正交相SnO₂ 的生长行为

王利军, 陈琛, 刘延雨, 陈志文

上海大学环境与化学工程学院射线应用研究所, 上海200444

收稿日期:2013-04-21 出版日期:2013-10-28 发布日期:2013-10-28
通讯作者: 陈志文(1962—), 男, 教授, 博士生导师, 博士, 研究方向为纳米材料的合成与性质. E-mail: zwchen@shu.edu.cn E-mail:zwchen@shu.edu.cn
作者简介:陈志文(1962—), 男, 教授, 博士生导师, 博士, 研究方向为纳米材料的合成与性质. E-mail: zwchen@shu.edu.cn
基金资助:
国家自然科学基金资助项目(11074161); 上海市科委基金资助项目(10JC1405400); 上海市重点学科建设资助项目(S30109)

Growth Behavior of Orthorhombic SnO₂ Induced by Mn-Doped SnO₂

WANG Li-jun, CHEN Chen, LIU Yan-yu, CHEN Zhi-wen

Applied Radiation Institute, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China

Received:2013-04-21 Online:2013-10-28 Published:2013-10-28

摘要/Abstract

摘要： 通过一种简单的共沉淀方法制备了Mn 掺杂二氧化锡(SnO₂)颗粒, 对前驱体在不同温度下热处理, 并通过X 射线衍射(X-ray diffraction, XRD)和高分辨电子显微学(high-resolution transmission electron microscopy,HRTEM)对样品的微纳米结构进行了表征. 结果表明: 样品中除了四方相SnO₂ 外, 还存在正交相SnO₂. XRD 测试结果显示, 随着退火温度的增加, 正交相SnO₂ 的峰强减弱, 四方相的峰强增加. HRTEM 分析表明: 样品中可以同时找到四方相和正交相SnO₂的晶格像, 进一步证实了正交相SnO₂的存在. Mn 掺杂SnO₂ 后, Mn 离子进入SnO₂晶胞, 替代了Sn 离子, 因此引起晶格扭曲畸变, 对正交相SnO₂的形成起着重要的作用.

关键词: 晶格畸变, 四方相, 微纳米结构, 正交相, 二氧化锡(SnO₂)

Abstract: Tin dioxide (SnO₂) is an n-type semiconductor material with tetragonal rutile crystal structure under normal conditions and displays many interesting physical and chemical properties. Another form of SnO₂with an orthorhombic crystal structure is known to be stable only at high pressures and temperatures. However, there are limited reports on effects of Mn-doped tetragonal phase SnO₂on micro/nanostructured characteristics. In this article, micro/nanostructures of Mn-doped tetragonal phase SnO₂ have been successfully prepared with a chemical co-precipitation method. The micro/nanostructural evolution of Mn-doped tetragonal phase SnO₂under different heat treatment temperatures is evaluated with X-ray diffraction (XRD) and a high-resolution transmission electron microscopy (HRTEM). It is surprisingly found that the orthorhombic phase SnO₂ is formed in Mn-doped tetragonal phase SnO₂. The obvious diffraction peaks and clear lattice fringes confirm that the orthorhombic phase SnO₂ nanocrystals evidently exist in Mn-doped SnO₂samples. Experimental results indicate that the XRD peak intensities and crystal planes of the orthorhombic phase SnO₂ decrease with increasing of heat treatment temperatures. Formation of orthorhombic phase SnO₂ is attributed to the lattice distortion of tetragonal phase SnO₂ due to the Mn-doped tetragonal phase SnO₂.

Key words: lattice distortion, micro-nanostructure, orthorhombic, tetragonal, tin dioxide (SnO₂)

中图分类号:

O 649.1

王利军, 陈琛, 刘延雨, 陈志文. 锰掺杂诱导正交相SnO₂ 的生长行为[J]. 上海大学学报(自然科学版), 2013, 13(5): 459-464.

WANG Li-jun, CHEN Chen, LIU Yan-yu, CHEN Zhi-wen. Growth Behavior of Orthorhombic SnO₂ Induced by Mn-Doped SnO₂[J]. Journal of Shanghai University（Natural Science Edition）, 2013, 13(5): 459-464.

参考文献

[1] Yusta F J, Hitchman M L, Shamlian S H. CVD preparation and characterization of tin dioxide films for electrochemical applications [J]. J Mater Chem,

1997, 7(8): 1421-1427.

[2] Wang J, Du J, Chen C, et al. Electron-beam irradiation strategies for growth behavior of tin dioxide nanocrystals [J]. J Phys Chem C, 2011, 115(42):

20523-20528.

[3] Huang H, Lim C K, Tse M S, et al. SnO₂ nanorod arrays: low temperature growth, surface modification and field emission properties [J]. Nanoscale, 2012,

4(5): 1491-1496.

[4] Zhou X M, Fu W Y, Yang H B, et al. Novel SnO₂ hierarchical nanostructures: synthesis and their gas sensing properties [J]. Mater Lett, 2012, 90: 53-55.

[5] Hossain M A, Jennings J R, Koh Z Y, et al. Carrier generation and collection in CdS/CdSe-sensitized SnO₂ solar cells exhibiting unprecedented photocurrent

densities [J]. ACS Nano, 2011, 5(4): 3172-3181.

[6] Chappel S, Chen S G, Zaban A. TiO2-coated nanoporous SnO₂ electrodes for dye-sensitized solar cells [J]. Langmuir, 2002, 18(8): 3336-3342.

[7] Renard L, Babot O, Saadaoui H, et al. Nanoscaled tin dioxide films processed from organotin-based hybrid materials: an organometallic

route toward metal oxide gas sensors [J]. Nanoscale, 2012, 4(21): 6806-6813.

[8] Kolmakov A, Klenov D O, Lilach Y, et al. Enhanced gas sensing by individual SnO₂ nanowires and nanobelts functionalized with Pdcatalystparticles [J].

Nano Lett, 2005, 5(4): 667-673.

[9] Du Z F, Yin X M, Zhang M, et al. In situ synthesis of SnO₂/graphene nanocomposite and their application as anode material for lithium ion battery [J].

Mater Lett, 2010, 64(19): 2076-2079.

[10] Wang X Y, Zhou X F, Yao K, et al. A SnO₂/graphene composite as a high stability electrode for lithium ion batteries [J]. Carbon, 2011,

49(1): 133-139.

[11] Dodd A, McKinley A, Saunders M, et al. Mechanochemical synthesis of nanocrystalline SnO₂-ZnO photocatalysts [J]. Nanotechnology, 2006, 17(3):

692-698.

[12] Lee J S, Sim S K, Min B, et al. Structural and optoelectronic properties of SnO₂nanowires synthesized from ball-milled SnO₂ powders [J]. J Cryst Growth,

2004, 267(1/2): 145-149.

[13] Woo H S, Hwang I S, Na C W, et al. Simple fabrication of transparent flexible devices using SnO₂nanowires and their optoelectronic properties [J].

Mater Lett, 2012, 68: 60-63.

[14] Chen Z W, Pan D Y, Zhao B, et al. Insight on fractal assessment strategies for tin dioxide thin films [J]. ACS Nano, 2010, 4(2): 1202-1208.

[15] Chen Z W, Wu C M L, Shek C H, et al. Pulsed laser ablation for tin dioxide: nucleation, growth, and microstructures [J]. Crit Rev Solid State Mater Sci,

2008, 33(3/4): 197-209.

[16] Zhang L S, Jiang L Y, Yan H J, et al. Mono dispersed SnO₂ nanoparticles on both sides of single layer graphene sheets as anode materials in Li-ion

batteries [J]. J Mater Chem, 2010, 20(26): 5462-5467.

[17] Singh M K, Mathpal M C, Agarwal A. Optical properties of SnO₂ quantum dots synthesized by laser ablation in liquid [J]. Chem Phys Lett, 2012, 536: 87-

91.

[18] Wang Y, Zeng H C, Lee J Y. Highly reversible lithium storage in porous SnO₂ nanotubes with coaxially grown carbon nanotube overlayers [J]. Adv

Mater, 2006, 18(5): 645-649.

[19] Chen Z W, Lai J K L, Shek C H. Insights into microstructural evolution from nanocrystalline SnO₂thin films prepared by pulsed laser deposition [J].

Phys Rev B, 2004, 70: 165314-1-165314-7.

[20] Meng X Q, Wu F M, Li J B. Study on optical properties of type-II SnO₂/ZnS core/shell nanowires [J]. J Phys Chem C, 2011, 115(15): 7225-7229.

[21] Ng H T, Li J, Smith M K, et al. Growth of epitaxial nanowires at the junctions of nanowalls [J]. Science, 2003, 300: 1249-1249.

[22] Cheng B, Russell J M, et al. Large-scale, solutionphase growth of single-crystalline SnO₂ nanorods [J]. J Am Chem Soc, 2004, 126: 5972-5973.

[23] Suito K, Kawai N, Masuda Y. High pressure synthesis of orthorhombic SnO₂ [J]. Mater Res Bull, 1975, 10(7): 677-680.

[24] Liu L G. A fluorite isotype of SnO₂ and a new modification of TiO₂: implications for the earth’s lower mantle [J]. Science, 1978, 199(4327): 422-425.
[25] Shek C H, Lai J K L, Lin G M, et al. Nanomicrostructure, chemical stability and abnormal transformation in ultrafine particles of oxidized tin [J]. J

Phys Chem Solids, 1997, 58(1): 13-17.

[26] Kaplan L, Ben-Shalom A, Boxman R L, et al. Annealing and Sb-doping of SnO films produced by filtered vacuum arc deposition: structure and electrooptical

properties [J]. Thin Solid Films, 1994, 253(1): 1-8.

[27] Kong L Y, Ma J, Zhu Z, et al. Synthesis of orthorhombic structure epitaxial tin oxide film [J]. Mater Lett, 2010, 64(12): 1350-1353.

[28] Chen Z W, Lai J K L, Shek C H. Facile strategy and mechanism for orthorhombic SnO₂ thin films [J]. Appl Phys Lett, 2006, 89(23): 231902.

[29] Hong N H, Sakai J, Prellier W, et al. Transparent Cr-doped SnO₂ thin films: ferromagnetism beyond room temperature with a giant magnetic moment

[J]. J Phys: Condens Matter, 2005, 17: 1697-1702.

[30] Tian Z M, Yuan S L, He J H, et al. Structure and magnetic properties in Mn doped SnO2 nanoparticles synthesized by chemical co-precipitation method [J].

J Alloys Compd, 2008, 466: 26-30.

[31] Sathyaseelan B, Senthilnathan K, Alagesan T, et al. A study on structural and optical properties of Mn- and Co-doped SnO₂ nanocrystallites [J]. Mater Chem Phys, 2010, 124(2/3): 1046-1050.

锰掺杂诱导正交相SnO₂ 的生长行为

Growth Behavior of Orthorhombic SnO₂ Induced by Mn-Doped SnO₂

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