射频磁控溅镀掺杂铜对钛酸锌薄膜中相变化及微结构的影响

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

  • 摘要: 探讨了ZnTiO3薄膜掺杂Cu元素对于薄膜性质、相变化与微结构之影响.实验是在一定温度下以射频磁控溅镀系统将铜沉积于ZnTiO3陶瓷靶上,控制沉积于ZnTiO3陶瓷靶上铜含量之后,再沉积掺杂铜的钛酸锌薄膜于SiO2/Si基板上.成长出来的薄膜经由ESCA分析得知铜的质量分数分别为0.84%、2.33%和2.84%.从XRD分析常温下掺杂Cu的ZnTiO3薄膜为非晶质态,经过600℃退火后,ZnTiO3薄膜则由非晶质态转变成Zn2Ti3O8结晶相,而未掺杂铜的ZnTiO3薄膜在600℃退火时并没有结晶相产生.ZnTiO3薄膜经过900℃退火后,Zn2Ti3O8相分解成Zn2TiO4相和TiO2相,且ZnTiO3晶格常数因为Cu离子置换至Zn离子的位置有变小的趋势.由TEM分析证实Cu离子与Zn离子的置换,导致晶格应变产生双晶缺陷.经由XRD、SEM和TEM分析得知掺杂太多的铜会抑制TiO2相的生成,而随着过多的Cu析出,晶体平均晶粒慢慢变小晶格应变也随之降低,以致晶格常数回复往原来晶格常数方向趋近.

     

    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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