两种方法制备花状ZnO纳米棒簇比较研究
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摘要
溶胶-凝胶法和水热法制备花状ZnO纳米棒簇,通过X射线衍射仪(XRD)、环境扫描电镜(ESEM)结合能谱仪(EDAX)、透射电子显微镜(TEM)、荧光光谱(PL)法对产物分析,并比较两种方法差异.得出如下结论:(1)两种均得到六方纤锌矿结构的ZnO纳米晶簇,晶型完整,粒径约300nm~500nm、长约0.5~3μm;XRD分析显示,ZnO晶体在[0002]晶面有强烈峰,表明其具有C轴最大生长速率和[0002]晶面最优生长习性.(2)不同之处:溶胶法晶粒末端呈锥形,而水热法呈正六边形;前者可用竹笋生长机理模型解释,而后者是从外到内逐层包覆生长机理模型.两种方法荧光光谱略有差异,水热法光谱红移更为显著.在370nm光激发后,两种方法获得材料均出现3个特征峰:凝胶法在424nm出现相对强而窄的紫带,而水热法在460nm出现蓝带峰.它们分别在587、590nm处呈相对弱而宽的黄绿带发射峰,在468、508nm附近也观察到弱的青蓝光发射.其中587、590nm是纳米ZnO的一个特征激发峰,与ZnO晶格中O空位Zn填隙离子有关,这是ZnO光致发光效应的一个重要依据.
Cauliflower-like ZnO nanometer clubclusters were prepared by sol-gel and hydrothermal methods.Products were analyzed by means of X-ray diffraction(XRD),environmental screening electron microscopy(ESEM)coupled with energy dispersive xray analysis(EDAX),and photoluminescence spectroscopy(PL).Differences of the two methods were compared.Conclusions were drawn:(1)Common grounds of two methods were that the as-synthesized nanocrystals were both hexagonal wurtzite structure with good crystallinity,the sizes were 300~500nm in diameter and 0.5~3μm in length.XRD analysis showed that there was a sharp diffraction peak for manys of ZnO nanorods in[0002]facet,which indicated that ZnO nanorods had a C-axis fastest grown rate or the preferred grown characteristic was in facet of[0002].(2)Differences were as follows:nanocrystals obtained by sol-gel method were cone-like in peaks,while,it took on regular hexagon prepared by hydrothermal method.The mechanisms of two methods were different,the former can be interpreted by bamboo-shoot growing model, the later was interpreted by stepwise coating model from exterior to interior.PL analysis showed that there was a little difference,PL spectrometry by hydrothermal method took on einstein shift:there was a strong and narrow ultraviolet band peak at 424nm by sol-gel method,while it was 460nm by hydrothermal method.Both of them had a weak and broad yellow-green band peak at 587,590nm,respectively,and a weaker cyanine band peak at 468,508nm when they were excited at wavelength of 370nm.Wherein, 587,590nm in wavelength was nano-ZnO characteristic emission peaks,which was launched by O space Zn interstitial associating defect to price jumps.That is an important foundation that ZnO nanocrystals have photoluminescence effect.
Cauliflower-like ZnO nanometer clubclusters were prepared by sol-gel and hydrothermal methods.Products were analyzed by means of X-ray diffraction(XRD),environmental screening electron microscopy(ESEM)coupled with energy dispersive xray analysis(EDAX),and photoluminescence spectroscopy(PL).Differences of the two methods were compared.Conclusions were drawn:(1)Common grounds of two methods were that the as-synthesized nanocrystals were both hexagonal wurtzite structure with good crystallinity,the sizes were 300~500nm in diameter and 0.5~3μm in length.XRD analysis showed that there was a sharp diffraction peak for manys of ZnO nanorods in[0002]facet,which indicated that ZnO nanorods had a C-axis fastest grown rate or the preferred grown characteristic was in facet of[0002].(2)Differences were as follows:nanocrystals obtained by sol-gel method were cone-like in peaks,while,it took on regular hexagon prepared by hydrothermal method.The mechanisms of two methods were different,the former can be interpreted by bamboo-shoot growing model, the later was interpreted by stepwise coating model from exterior to interior.PL analysis showed that there was a little difference,PL spectrometry by hydrothermal method took on einstein shift:there was a strong and narrow ultraviolet band peak at 424nm by sol-gel method,while it was 460nm by hydrothermal method.Both of them had a weak and broad yellow-green band peak at 587,590nm,respectively,and a weaker cyanine band peak at 468,508nm when they were excited at wavelength of 370nm.Wherein, 587,590nm in wavelength was nano-ZnO characteristic emission peaks,which was launched by O space Zn interstitial associating defect to price jumps.That is an important foundation that ZnO nanocrystals have photoluminescence effect.
引文
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[19]傅竹西,林碧霞,郭常新,等.氧化锌半导体薄膜的发光光谱特性[J].半导体学报,1999,20(9):827-830.
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[21]黄金昭,李世帅,冯秀鹏.ZnO纳米棒的低温溶液法制备、光电特性研究及其在有机/无机复合电致发光中的应用[J].物理学报,2010,59(8):5840-5845.
[2]Dillon A C,Jones K M,Bekkedahl T A,et al.Storage of hydrogen in single-walled carbon nanotubes[J].Nature,1997,386:377-379.
[3]Michael H H,Samuel M,Henning F.Room-temperature ultraviolet nanowire nanolasers[J].Science,2001,292:1897-1899.
[4]俞建群,贾殿增,郑毓峰.纳米氧化镍和氧化锌的合成新方法[J].无机化学学报,1999,15(1):95-98.
[5]Vayssieres L.Growth of arrayed nanorods and nanowires of ZnO from aqueous solution[J].Advanced Materials,2003,15(5):464-466.
[6]Kong X Y,Ding Y,Yang R S,et al.Single-crystal nanorings formed by epitaxial self-coiling of qolar nanobelts[J].Science(S0036-8075),2004,303:1348-1351.
[7]方国家,王明军,刘逆霜,等.ZnO纳米线阵列的定向生长、光致发光及场发射性能[J].发光学报,2008,29(3):421-424.
[8]陈建刚,郭常新,张琳丽,等.一步溶液法制备ZnO亚微米晶体棒及其发光性能[J].发光学报,2006,27(1):59-65.
[9]Zhang H,Yang D R,Ji Y J,et al.Low temperature synthesis of flower like ZnO nanostructures by cetyltrim ethylammonium bromide-assisted hydrothermal process[J].Journal of Physical Chemistry B,2004,108(13):3955-3958.
[10]Tokumoto M S,Pulcinelli S H,Santillic C V,et al.Catalysis and temperature dependence on the formation of ZnO nanoparticles and of zinc acetate derivatives prepared by the sol-gel route[J].Journal of Physical Chemistry B,2003,107:568-574.
[11]石礼伟,李玉国,王强,等.热氧化磁控溅射金属锌膜制备ZnO纳米棒[J].固体电子学研究与进展,2004,24(4):432-435.
[12]黄运华,贺建,张跃,等.梳状氧化锌纳米材料的制备及结构、性能的表征[J].功能材料与器件学报,2005,11(3):278-281.
[13]张月,高艳阳.室温固相法合成ZnO纳米棒及其光学特性[J].功能材料与器件学报,2006,12(4):343-346.
[14]季振国,宋永梁,杨成兴,等.溶胶-凝胶法制备ZnO薄膜及表征[J].半导体学报,2004,25(1):52-55.
[15]黄雪锋,唐玉朝,黄显怀,等.水热法制备N掺杂纳米TiO2及其光催化活性研究[J].环境化学,2006,25(1):16-19.
[16]杨枣.一维ZnO纳米结构的制备、性能和器件研究[D].长沙:湖南大学,2008.
[17]刘长友,李焕勇,介万奇.水热法制备菜花状氧化锌[J].功能材料,2005,36(11):1753-1756.
[18]张现利,李村,吴振玉,等.纳米氧化锌的室温合成及表征[J].广东化工,2009,36(8):3-5.
[19]傅竹西,林碧霞,郭常新,等.氧化锌半导体薄膜的发光光谱特性[J].半导体学报,1999,20(9):827-830.
[20]Vanheusden K,Warren W L,Seager C H,et al.Mechanisms behind green photoluminescence in ZnO phosphor powders[J].Journal of Applied Physics,1996,79(10):7983-7990.
[21]黄金昭,李世帅,冯秀鹏.ZnO纳米棒的低温溶液法制备、光电特性研究及其在有机/无机复合电致发光中的应用[J].物理学报,2010,59(8):5840-5845.