立方形貌ITO粉体的水热法制备及光电性能

doi:10.7503/cjcu20170046

摘要/Abstract

摘要：

以金属In和SnCl₄·5H₂O为原料, 采用水热法在120~140 ℃得到In(OH)₃前驱体, 该前驱体在550 ℃下煅烧得到立方体形貌的氧化铟锡粉体. 研究了水热反应温度和反应时间对粉体形貌和晶型的影响. 通过热分析仪(TG-DSC)、 X射线衍射仪(XRD)、拉曼光谱仪(Raman)、透射电子显微镜(TEM)、四探针电阻仪、 X射线光电子能谱仪(XPS)、紫外-可见-近红外分光光度计以及荧光光谱仪对粉体进行了表征, 并对水热反应条件为140 ℃及12 h下制备的c-ITO的光电性能进行了分析. 结果表明, 随着水热反应温度的升高, ITO粉体形貌由立方体向不规则形貌转变, 粉体晶型出现少量的六方相. 在水热反应条件为140 ℃, 12 h, 铟离子与尿素的摩尔比为1∶5 时, 得到平均粒径为230 nm的立方体ITO粉体, 其电阻率为1.247 Ω·cm, 光学能带间隙为3.685 eV, 与c-In₂O₃相比其能带间隙更高, 室温下260 nm激发波长下粉体出现光致发光, 发射峰位于蓝光区域.

关键词: 立方体形貌氧化铟锡, 水热法, 光电性能

Abstract:

Cubic indium tin oxide(c-ITO) nanopowders were prepared by hydrothermal method under 120—140 ℃ to get the precursor and calcination at 550 ℃, using metal In and SnCl₄·5H₂O as the raw materials. The hydrothermal temperature and the reaction time influenced the morphology and the crystal structure of the ITO powders. The photoelectric performance of the c-ITO prepared under 140 ℃ for 12 h was analyzed. The ITO powders were also characterized by means of thermogravimetric-differential scanning calorimetry(TG-DSC) analysis, X-ray diffraction(XRD), Raman spectroscopy, transmission electron microscopy(SEM), four point probe resistance measurement, X-ray photoelectron spectroscopy(XPS) and UV-Vis spectrophotometry(UV-Vis). The results show that with the increase of hydrothermal temperature, ITO powders’ morphology changed from cubic to irregular shape, and a small amount of hexagonal phase crystal appeared. The average size of the c-ITO prepared after hydrothermal treatment at 140 ℃ for 12 h with n(In³⁺)∶n[CO(NH₂)₂]=1∶5 was 230 nm, and the c-ITO showed a better electrical performance with a low resistivity of 1.247 Ω·cm. Compared with c-In₂O₃, c-ITO has a higher optical band gap of 3.685 eV. The PL spectrum of c-ITO excitated with 260 nm wavelength was in blue light region.

Key words: Cubic indium tin oxide, Hydrothermal method, Photoelectric property

中图分类号:

O611

TrendMD:

张怡青, 刘家祥. 立方形貌ITO粉体的水热法制备及光电性能. 高等学校化学学报, 2017, 38(7): 1110.

ZHANG Yiqing, LIU Jiaxiang. Hydrothermal Preparation of Cubic ITO Powder and Its Photoelectric Performance^†. Chem. J. Chinese Universities, 2017, 38(7): 1110.

图/表 10

Fig.1 TG-DSC curves of ITO precursor obtained under 140 ℃ hydrothermal reaction

Fig.2 XRD patterns of products prepared under different temperaturesa. 120 ℃, ITO; b. 140 ℃, ITO; c. 160 ℃, ITO; d. 140 ℃, In(OH)3.

Fig.3 Raman spectrum of ITO powder obtained after 140 ℃ hydrothermal treatmentΓopt=4Ag+4Eg+14Tg+5Au+5Eu+16Tu(6)

Fig.4 TEM images of ITO powders prepared after different hydrothermal treatment (A) 120 ℃, 6 h; (B) and (C) 140 ℃, 6 h; (D) and (E) 140 ℃, 12 h; (F) 160 ℃, 6 h.

Fig.5 XPS spectra of ITO powder obtained after hydrothermal treatment at 140 ℃ for 12 h (A) Wide scan; (B) narrow scan of O1s; (C) narrow scan of In3d; (D) narrow scan of Sn3d.

Fig.6 Resistivity of ITO powders prepared after hydrothermal treatment at 120 ℃ for 6 hn(In3+)∶n[CO(NH2)2]: a. 1∶3; b. 1∶4; c. 1∶5; d. 1∶6.

Fig.7 Resistivity of ITO powders prepared after different hydrothermal treatmenta. 120 ℃, 6 h; b. 140 ℃, 6 h; c. 140 ℃, 12 h; d. 160 ℃, 6 h.

Fig.8 Diffusion reflection spectrum of ITO powder obtained after hydrothermal treatment at 140 ℃ for 12 h

Fig.9 UV-Vis absorption spectrum of ITO powder obtained after hydrothermal treatment at 140 ℃ for 12 hInset: the corresponding plot of (αhv)2 as a function of photon energy(hv).

Fig.10 Photoluminescence spectrum of ITO nanopowders

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