氧化铪基铁电薄膜相结构调控的研究进展

Research progress on phase structure regulation of hafnium oxide-based ferroelectric thin films

  • 摘要: 随着微电子技术的发展,氧化铪(HfO2)因具有与Si基半导体工艺相兼容、适宜的相对介电常数、良好的热稳定性和化学稳定性以及较大的禁带宽度等优点,成为当前新型铁电材料的研究焦点. HfO2是一种典型的“相结构决定性能,性能决定应用”的材料,其铁电性能源于薄膜中存在空间点群为Pca21的非中心对称的正交相. 因此,实现HfO2薄膜铁电性能稳定与提升的前提是调控HfO2薄膜于亚稳正交相结构. 以正交相的调控机理为出发点,综述了HfO2正交相的稳定因素,并分别从薄膜厚度、掺杂元素、退火工艺、晶粒取向和电极材料等方面进行归纳,例如HfO2材料的正交相含量随薄膜厚度的增加而降低;适宜含量的元素掺杂可以稳定HfO2材料的正交相;高的升温速率,极短的退火时间可抑制单斜相的形成;制备具有特定取向的正交相薄膜以及顶部电极的夹持作用都是保证HfO2材料正交相稳定的重要因素. 最后,对HfO2薄膜未来发展做出展望.

     

    Abstract: With the development of microelectronics technology, hafnium oxide (HfO2) has become the research focus of new ferroelectric materials because of its compatibility with Si-based semiconductor technology, suitable relative dielectric constant, good thermal and chemical stabilities, and a large band gap. HfO2 is a typical material that “phase structure determines properties, and properties determine applications.” The ferroelectric property is confirmed by the fact that the phase structure of thin films is stable in a noncentrosymmetric Pca21 orthorhombic phase. Therefore, the prerequisite for stabilizing and improving the ferroelectric properties of HfO2 thin films is to regulate HfO2 in the metastable orthorhombic phase. In general, HfO2 films can be composed of multiple phases, such as the monoclinic, orthorhombic, and tetragonal (or cubic) phases. Among these, the tetragonal phase is the parent phase of the orthogonal and monoclinic phases, and there is no possibility of phase transformation between the orthogonal and monoclinic phases. Therefore, a consensus is reached in the actual phase structure regulation of HfO2 thin films, that is, inhibiting the monoclinic phase formation can also improve the ferroelectric properties of thin films. Considering the orthogonal phase regulation mechanism, the stability factors of the orthogonal phase in HfO2 thin films are reviewed and summarized based on aspects such as film thickness, doping elements, grain orientation, annealing process, and electrode materials. For instance, the orthogonal phase content of HfO2 thin films decreases with the increase of film thickness; appropriate content of element doping can stabilize the orthogonal phase of HfO2 thin films. Both the high heating rate and short annealing time during the heat treatment are important factors in ensuring the orthogonal stability of HfO2 films. Especially, strain also affects the phase structure regulation. First, top electrode clamping can stabilize thin HfO2 films in the orthogonal phase by applying force on the films. Second, thin HfO2 films with a single orientation can be obtained through epitaxial growth, and it can be well observed how the strain regulates the thin film phase structure; that is, applying the tensile strain to the thin film is an effective means to stabilize the orthogonal phase. Simultaneously, with successful HfO2 film preparation with several atomic layers, it is revealed that the rhombohedral phase has out-of-plane spontaneous polarization and ferroelectric properties with compressive strain generation. Finally, the future prospects of thin HfO2 film development are discussed in this paper.

     

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