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射頻磁控濺鍍摻雜銅對鈦酸鋅薄膜中相變化及微結構的影響

Influence of Cu doping on the phase transformation and microstructure of zinc titanate thin films by RF magnetron sputtering

  • 摘要: 探討了ZnTiO3薄膜摻雜Cu元素對于薄膜性質、相變化與微結構之影響.實驗是在一定溫度下以射頻磁控濺鍍系統將銅沉積于ZnTiO3陶瓷靶上,控制沉積于ZnTiO3陶瓷靶上銅含量之后,再沉積摻雜銅的鈦酸鋅薄膜于SiO2/Si基板上.成長出來的薄膜經由ESCA分析得知銅的質量分數分別為0.84%、2.33%和2.84%.從XRD分析常溫下摻雜Cu的ZnTiO3薄膜為非晶質態,經過600℃退火后,ZnTiO3薄膜則由非晶質態轉變成Zn2Ti3O8結晶相,而未摻雜銅的ZnTiO3薄膜在600℃退火時并沒有結晶相產生.ZnTiO3薄膜經過900℃退火后,Zn2Ti3O8相分解成Zn2TiO4相和TiO2相,且ZnTiO3晶格常數因為Cu離子置換至Zn離子的位置有變小的趨勢.由TEM分析證實Cu離子與Zn離子的置換,導致晶格應變產生雙晶缺陷.經由XRD、SEM和TEM分析得知摻雜太多的銅會抑制TiO2相的生成,而隨著過多的Cu析出,晶體平均晶粒慢慢變小晶格應變也隨之降低,以致晶格常數回復往原來晶格常數方向趨近.

     

    Abstract: The influence of Cu doping on the properties, phase transformation and microstructure of ZnTiO3 films was investigate. Experiments were performed with Cu depositing on ZnTiO3 ceramic targets by RF magnetron sputtering at substrate temperatures, and by controlling the Cu content, different Cu-doped ZnTiO3 films were deposited on SiO2/Si substrates. ESCA analysis shows that the mass fractions of Cu in the Cu-doped ZnTiO3 films are 0. 84%, 2. 33%, and 2. 84%. XRD analysis reveals that the Cu-doped ZnTiO3 films are amorphous at normal temperature;
    after annealed at 600℃ the films transforms from amorphous to Zn2Ti3O8 crystalline phase, but there is no crystalline phase in the pure ZnTiO3 film annealed at 600℃. The Zn2Ti3O8 phase decomposes into Zn2TiO4 phase and TiO2 phase, and the lattice of ZnTiO3 changes little because the Zn2+ position is replaced by Cu ions when annealing at 900℃. XRD, SEM and TEM analyses show that the formation of TiO2 phase would be inhibited when doping too much Cu. When Cu2+ substitutes for Zn2+ in an ABO3 structure, it leads to the formation of twin-crystals which is attributed to the lattice strain. This result can be confirmed by TEM analysis. With the precipitation of excessive Cu, the average grain size gradually becomes small and the lattice strain is also decreased, so that the lattice constant returns to the original level.

     

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