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Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO_2 surfaces Ⅲ. Ni on TiO_2(001) and Cu on TiO_2(110)

机译:TiO_2表面过渡金属覆盖层电子结构改性的光发射研究Ⅲ。 TiO_2(001)上的Ni和TiO_2(110)上的Cu

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The electronic states of the Ni overlayers on TiO_2(001) surfcace and Cu overlayers on TiO_2(110) surface have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. In the Ni/ TiO_2(001) system, an in-gap emission from the reduced Ti~(3+) 3d~1 state appears at 1.2 eV below EF for the initial Ni deposition. Upon further deposition, the emission grows and is evolved to a spectrum of Ni metal, with forming no Fermi edge, suggesting the formation of small Ni clusters on TiO_2(001). In the Cu/TiO_2(110) system, Cu grows in a Stranski-Krastanov mode. Two in-gap emissions from the reduced Ti~(3+) 3d~1 state and oxidized Cu~+ 3d~(10) or Cu~(2+) 3d~9 state are observed at 0.8 and 2.8 eV below E_F, respectively, for the initial Cu deposition, giving convincing evidence that there is significant charge transfer between Cu and the substrate. Upon further deposition, the emission in the band-gap region is evolved to a spectrum of Cu metal, though delayed completion of the Fermi edge is observed. Such delay can be explained by finite cluster size effects.
机译:利用角度分辨和共振光电子能谱研究了同步加速器辐射下TiO_2(001)表面上的Ni覆盖层和TiO_2(110)表面上的Cu覆盖层的电子态。在Ni / TiO_2(001)系统中,还原的Ti〜(3+)3d〜1态的能隙发射在EF下方1.2 eV处出现,用于初始Ni沉积。进一步沉积后,发射物逐渐生长并演化为镍金属光谱,没有形成费米边缘,这表明在TiO_2(001)上形成了小的镍簇。在Cu / TiO_2(110)系统中,Cu以Stranski-Krastanov模式生长。在E_F以下0.8和2.8 eV处分别观察到了还原的Ti〜(3+)3d〜1状态和氧化的Cu〜+ 3d〜(10)或Cu〜(2+)3d〜9状态的两个能隙发射。 ,对于初始的Cu沉积而言,令人信服的证据表明Cu与衬底之间存在大量电荷转移。在进一步沉积时,尽管观察到费米边缘的延迟完成,但是带隙区域中的发射演化为铜金属的光谱。这种延迟可以通过有限的簇大小效应来解释。

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