采用脉冲激光沉积术(PLD)同质外延生长了表面原子级平整的6%(原子比)Cr掺杂的金红石相TiO2(110)单晶薄膜,采用扫描隧道显微镜(STM)、扫描隧道谱(STS)、X射线光电子能谱(xPS)和紫外光电子能谱(UPS)对其进行了表征.结果表明:Cr掺杂对TiO2(110)-(1×1)表面的形貌没有明显影响,但是提高了掺杂薄膜在负偏压的导电性:Cr与晶格O键合而呈现+3价态,由此在TiO2的价带顶上方-0.4eV处引入杂质能级.紫外.可见光吸收谱显示薄膜的光吸收能力被扩展到-650nm,处于可见光范围.借助STM以单个甲醇分子的光解反应检测了薄膜的光催化活性.仅观察到紫外光照射下甲醇分子的脱氢反应,在可见光照射下(A〉430nm)甲醇分子没有发生反应,表明单独的Cr掺杂可能不足以提高TiO2在可见光下的催化活性.
The growth of Cr-doped rutile TIO2(110) homoepitaxial single crystal thin films using the pulsed laser deposition (PLD) method was investigated. Surface morphology and electronic structure were characterized using scanning tunneling microscopy/spectroscopy (STM/STS), and X-ray and ultraviolet photoemission spectroscopies (XPS/UPS). Optical absorption spectra were measured using ultraviolet- visible (UV-Vis) absorption spectroscopy. STM images revealed that the atomically flat TIO2(110)-(1 × 1) surface was maintained at a Cr doping concentration of 6% (atomic ratio), indicating that the Cr dopant had negligible effect on surface morphology. The Cr-doped rutile TIO2(110) film showed higher tunneling conductance than an undoped rutile single crystal. XPS and UPS spectra indicated that Cr atoms bound to lattice O, were present in + 3 oxidation state and introduced an impurity state 0.4 eV above the valence band maximum. The UV-Vis absorption spectrum of the Cr-doped film showed an absorbance extending to -650 nm in the visible range, which was consistent with UPS measurements. Using the Cr-doped TiO2 films, the dissociation of methanol molecules was only observed under irradiation with UV light (wavelength shorter than 430 nm). The dissociation reaction was not observed under irradiation with visible light (wavelength longer than 430 nm). Our results suggest that doping with Cr element alone may not be sufficient to promote the visible light photoactivity of rutile TIO2(110) surfaces.