Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy

Gu, Yiyi; Zhang, Lizhi; Cai, Hui; Liang, Liangbo; Liu, Chenze; Hoffmann, Anna; Yu, Yiling; Houston, Austin; Puretzky, Alexander A.; Duscher, Gerd; Rack, Philip D.; Rouleau, Christopher M.; Meng, Xiangmin; Yoon, Mina; Geohegan, David B.; Xiao, Kai

doi:10.1021/acsnano.2c02711

Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe₂ Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy

Journal Article · Fri Jul 01 00:00:00 EDT 2022 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.2c02711· OSTI ID:1890338

Gu, Yiyi ^[1]; Zhang, Lizhi ^[2]; Cai, Hui ^[3]; ^[3]; ^[3]; ^[4]; ^[3]; Houston, Austin ^[4]; ^[3]; Duscher, Gerd ^[4]; ^[4]; ^[3]; Meng, Xiangmin ^[5]; ^[3]; ^[3]; ^[3]

Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Tennessee, Knoxville, TN (United States); University of Chinese Academy of Sciences, Beijing (China)
Univ. of Tennessee, Knoxville, TN (United States); National Center for Nanoscience and Technology of China, Beijing (China)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)

PdSe₂ has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se–Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe₂ is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe₂. Monoclinic PdSe₂ is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. Further, the structure and composition of the monoclinic PdSe₂ crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe₂ flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe₂ exhibits n-type charge carrier conduction with electron mobilities up to ~298 cm² V^–1 s^–1 and a strong in-plane electron mobility anisotropy of ~1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1890338

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 9 Vol. 16; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy

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Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe₂ Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy