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1. 国家纳米科学中心 北京,100190
2. 中国科学院, 物理研究所 北京,100080
3. 美国佐治亚理工学院 亚特兰大,30332-0245
收稿日期:2007-10-25,
修回日期:2007-12-24,
纸质出版日期:2008-05-20
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武祥, 江鹏, 解思深, 王中林. 弯曲表面上ZnO亚微米棒阵列的制备[J]. 发光学报, 2008,29(3): 475-478
WU Xiang, JIANG Peng, XIE Si-shen, WANG Zhong-lin, . Preparation of ZnO Sub-micrometer Rod Arrays on Bent Surface of Zn Microspheres[J]. Chinese Journal of Luminescence, 2008,29(3): 475-478
以ZnS和金属Zn粉末混合物为蒸发源以及金属Zn片为衬底
利用热蒸发气相沉积方法
在弯曲的金属Zn微球表面上
成功地获得了ZnO亚微米棒阵列结构。场发射扫描电镜研究表明:在弯曲的Zn微球表面
能自组织地生长出大量的截面为六边形的ZnO亚微米棒
这些亚微米棒的平均直径为500nm
长约1μm。棒的顶部是平滑的。能量散射X射线谱结果表明:合成的产品只存在Zn和O两种元素
其成分比例接近1:1。没有观察到S元素。光致发射(PL)光谱显示:在387nm紫外波长处
出现一个强的半峰全宽为16nm的窄发光峰
可归属于ZnO的近带边发光
而509nm左右较弱的宽峰则源于界面缺陷态发光。这些研究结果说明我们所合成的这种ZnO亚微米棒阵列材料在紫外受激发射器件方面有着潜在的应用价值。
ZnO sub-micrometer rod arrays have been prepared on bent surface of Zn microspheres by thermal evaporating the mixture of ZnS and Zn powder to metal Zn slice. In a typical preparation process
0.01 mol ZnS and 0.01 mol Zn powder were mixed in an aluminum boat and positioned at the center of a horizontal quarts tube furnace. A slice of metal Zn substrate in a small quartz boat was located in downstream region of the tube. The whole system was sealed and pumped to a pressure of 100 Pa. High-purity Ar was aerated into the tube at a flow rate of 100 standard cubic centimeters per minute. The pressure in the tube was kept at 0.04 MPa. The furnace temperature was heated up to 900℃ at a 20℃/min rate. The system was kept at 900℃ for 2h. After the furnace was cooled to room temperature naturally
white wool-like matter was found to deposit on the Zn substrate. Finally
the product was collected for further characterizations by field-emission scanning electron microscope (FE-SEM
Hitachi S-4800) and LEO 1550 SEM attached with an Oxford Inca Drycool EDS detector. The results show ZnO sub-micrometer rod arrays can self-organized grow on surfaces of formed Zn microspheres. These ZnO rods with hexagonal cross-section have an average diameter of 500 nm and length of 1 μm. Top of the ZnO rod is very flat. Energy dispersive X-ray spectrum of the ZnO rod array demonstrates that only Zn and O elements exist with a ratio of about 1:1. No S element has been found. ZnO crystal exhibits hexagonal wurtzite structure
which belongs to the space group
C
4V
6
. According to selection rule of phonon mode
Raman active modes for the wurtzite ZnO are: 1A
1
+2B
2
+1E
1
+2E
2
. A
1
and E
1
modes are polar and can split into the transverse optical (TO) and longitudinal optical (LO) phonon modes. E
2
mode is non-polar optical phonon mode
which is composed of two modes with low and high frequency. The vibration peaks at 331
381
430 and 580 cm
-1
can be clearly observed in Raman spectrum of the ZnO sub-micrometer rod array. The peaks at 381 and 580 cm
-1
correspond to polar transverse A
1
and longitudinal E
1
optical phonon modes
respectively. The strong peak at 430 cm
-1
can be assigned to the nonpolar optical phonon (E
2
) modes of the ZnO rod at high frequency
which is associated with oxygen deficiency. The peak at 331 cm
-1
is attributed to the 2E
2
mode. Photoluminescence spectra of the ZnO rod arrays show two peaks at the wavelength of 387 nm and 509 nm
respectively. The stronger peak at 387 nm with the full width at half maximum (FWHM) of 16 nm can be attributed to near band-edge emission. Another weaker peak at 509 nm probably is due to defect state luminescence. The sub-micrometer ZnO rod arrays have a potential application in ultraviolet laser devices.
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