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氧化鉿基鐵電薄膜相結構調控的研究進展

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

  • 摘要: 隨著微電子技術的發展,氧化鉿(HfO2)因具有與Si基半導體工藝相兼容、適宜的相對介電常數、良好的熱穩定性和化學穩定性以及較大的禁帶寬度等優點,成為當前新型鐵電材料的研究焦點. HfO2是一種典型的“相結構決定性能,性能決定應用”的材料,其鐵電性能源于薄膜中存在空間點群為Pca21的非中心對稱的正交相. 因此,實現HfO2薄膜鐵電性能穩定與提升的前提是調控HfO2薄膜于亞穩正交相結構. 以正交相的調控機理為出發點,綜述了HfO2正交相的穩定因素,并分別從薄膜厚度、摻雜元素、退火工藝、晶粒取向和電極材料等方面進行歸納,例如HfO2材料的正交相含量隨薄膜厚度的增加而降低;適宜含量的元素摻雜可以穩定HfO2材料的正交相;高的升溫速率,極短的退火時間可抑制單斜相的形成;制備具有特定取向的正交相薄膜以及頂部電極的夾持作用都是保證HfO2材料正交相穩定的重要因素. 最后,對HfO2薄膜未來發展做出展望.

     

    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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