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

Title: 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];

^[4];

^[3]; Houston, Austin ^[4];

^[3]; Duscher, Gerd ^[4];

^[4];

^[3]; Meng, Xiangmin ^[5];

^[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.

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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:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1890338

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

Crystal Structures of the High‐Pressure Palladium Dichalcogenides Pd _0.94(1) S ₂ and Pd _0.88(1) Se ₂ Comprising Exceptional Pd ^IV Oxidation States Selb, Elisabeth; Götsch, Thomas; Janka, Oliver Zeitschrift für anorganische und allgemeine Chemie, Vol. 643, Issue 21 https://doi.org/10.1002/zaac.201700140	journal	July 2017
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Construction of bilayer PdSe2 on epitaxial graphene Li, En; Wang, Dongfei; Fan, Peng Nano Research, Vol. 11, Issue 11 https://doi.org/10.1007/s12274-018-2090-0	journal	May 2018
Ferroelastic lattice rotation and band-gap engineering in quasi 2D layered-structure PdSe 2 under uniaxial stress Lei, Wen; Cai, Bo; Zhou, Huanfu Nanoscale, Vol. 11, Issue 25 https://doi.org/10.1039/C9NR03101D	journal	January 2019
In-Plane 2H-1T′ MoTe ₂ Homojunctions Synthesized by Flux-Controlled Phase Engineering Yoo, Youngdong; DeGregorio, Zachary P.; Su, Yang Advanced Materials, Vol. 29, Issue 16 https://doi.org/10.1002/adma.201605461	journal	February 2017
A new 2D high-pressure phase of PdSe ₂ with high-mobility transport anisotropy for photovoltaic applications Lei, Wen; Zhang, Shengli; Heymann, Gunter Journal of Materials Chemistry C, Vol. 7, Issue 7 https://doi.org/10.1039/C8TC06050A	journal	January 2019
Phase-controlled epitaxial growth of MoTe₂: Approaching high-quality 2D materials for electronic devices with low contact resistance Tao, Li; Zhou, Yaoqiang; Xu, Jian-Bin Journal of Applied Physics, Vol. 131, Issue 11 https://doi.org/10.1063/5.0073650	journal	March 2022
Discovering two-dimensional topological insulators from high-throughput computations Olsen, Thomas; Andersen, Erik; Okugawa, Takuya Physical Review Materials, Vol. 3, Issue 2 https://doi.org/10.1103/PhysRevMaterials.3.024005	journal	February 2019
Influence of channel thickness on charge transport behavior of multi-layer indium selenide (InSe) field-effect transistors Wasala, Milinda; Patil, Prasanna D.; Ghosh, Sujoy 2D Materials, Vol. 7, Issue 2 https://doi.org/10.1088/2053-1583/ab6f79	journal	February 2020
Layer-dependent optical and dielectric properties of centimeter-scale PdSe2 films grown by chemical vapor deposition Wei, MingYang; Lian, Jie; Zhang, Yu npj 2D Materials and Applications, Vol. 6, Issue 1 https://doi.org/10.1038/s41699-021-00282-5	journal	January 2022
Millimeter-Scale Single-Crystalline Semiconducting MoTe ₂ via Solid-to-Solid Phase Transformation Xu, Xiaolong; Chen, Shulin; Liu, Shuai Journal of the American Chemical Society, Vol. 141, Issue 5 https://doi.org/10.1021/jacs.8b12230	journal	January 2019
Pentagonal two-dimensional noble-metal dichalcogenide PdSSe for photocatalytic water splitting with pronounced optical absorption and ultrahigh anisotropic carrier mobility Xiao, Feng; Lei, Wen; Wang, Wei Journal of Materials Chemistry C, Vol. 9, Issue 24 https://doi.org/10.1039/D1TC01245B	journal	January 2021
Synthesis of High-Quality Large-Area Homogenous 1T′ MoTe ₂ from Chemical Vapor Deposition Zhou, Lin; Zubair, Ahmad; Wang, Ziqiang Advanced Materials, Vol. 28, Issue 43 https://doi.org/10.1002/adma.201602687	journal	September 2016
Mobility engineering and a metal–insulator transition in monolayer MoS2 Radisavljevic, Branimir; Kis, Andras Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3687	journal	June 2013
Room Temperature Semiconductor–Metal Transition of MoTe ₂ Thin Films Engineered by Strain Song, Seunghyun; Keum, Dong Hoon; Cho, Suyeon Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b03481	journal	December 2015
Phase patterning for ohmic homojunction contact in MoTe2 Cho, S.; Kim, S.; Kim, J. H. Science, Vol. 349, Issue 6248 https://doi.org/10.1126/science.aab3175	journal	August 2015
PdSe ₂ : Pentagonal Two-Dimensional Layers with High Air Stability for Electronics Oyedele, Akinola D.; Yang, Shize; Liang, Liangbo Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b04865	journal	September 2017
Tellurization Velocity-Dependent Metallic–Semiconducting–Metallic Phase Evolution in Chemical Vapor Deposition Growth of Large-Area, Few-Layer MoTe ₂ Yang, Li; Zhang, Wenfeng; Li, Jie ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b08109	journal	February 2017
Verbeekite, the Long-Unknown Crystal Structure of Monoclinic PdSe ₂ Selb, Elisabeth; Tribus, Martina; Heymann, Gunter Inorganic Chemistry, Vol. 56, Issue 10 https://doi.org/10.1021/acs.inorgchem.7b00544	journal	April 2017
Electric-field induced structural transition in vertical MoTe2- and Mo1–xWxTe2-based resistive memories Zhang, Feng; Zhang, Huairuo; Krylyuk, Sergiy Nature Materials, Vol. 18, Issue 1 https://doi.org/10.1038/s41563-018-0234-y	journal	December 2018
High‐Performance, Room Temperature, Ultra‐Broadband Photodetectors Based on Air‐Stable PdSe ₂ Liang, Qijie; Wang, Qixing; Zhang, Qian Advanced Materials https://doi.org/10.1002/adma.201807609	journal	April 2019
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
High Mobility 2D Palladium Diselenide Field-Effect Transistors with Tunable Ambipolar Characteristics Chow, Wai Leong; Yu, Peng; Liu, Fucai Advanced Materials, Vol. 29, Issue 21 https://doi.org/10.1002/adma.201602969	journal	April 2017
Anomalous interlayer vibrations in strongly coupled layered PdSe ₂ Puretzky, Alexander A.; Oyedele, Akinola D.; Xiao, Kai 2D Materials, Vol. 5, Issue 3 https://doi.org/10.1088/2053-1583/aabe4d	journal	May 2018
Ubiquitous formation of bulk Dirac cones and topological surface states from a single orbital manifold in transition-metal dichalcogenides Bahramy, M. S.; Clark, O. J.; Yang, B. -J. Nature Materials, Vol. 17, Issue 1 https://doi.org/10.1038/nmat5031	journal	November 2017
Structural phase transition in monolayer MoTe2 driven by electrostatic doping Wang, Ying; Xiao, Jun; Zhu, Hanyu Nature, Vol. 550, Issue 7677 https://doi.org/10.1038/nature24043	journal	October 2017
Vapor phase growth of two-dimensional PdSe2 nanosheets for high-photoresponsivity near-infrared photodetectors Xu, Weiting; Jiang, Jiayang; Ma, Huifang Nano Research, Vol. 13, Issue 8 https://doi.org/10.1007/s12274-020-2815-8	journal	May 2020
Two‐Dimensional Palladium Diselenide with Strong In‐Plane Optical Anisotropy and High Mobility Grown by Chemical Vapor Deposition Gu, Yiyi; Cai, Hui; Dong, Jichen Advanced Materials, Vol. 32, Issue 19 https://doi.org/10.1002/adma.201906238	journal	March 2020
Type-II Weyl semimetals Soluyanov, Alexey A.; Gresch, Dominik; Wang, Zhijun Nature, Vol. 527, Issue 7579 https://doi.org/10.1038/nature15768	journal	November 2015
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Verbeekite, monoclinic PdSe₂, a new mineral from the Musonoi Cu-Co-Mn-U mine, near Kolwezi, Shaba Province, Democratic Republic of Congo Roberts, A. C.; Paar, W. H.; Cooper, M. A. Mineralogical Magazine, Vol. 66, Issue 1 https://doi.org/10.1180/0026461026610020	journal	February 2002
PdSe ₂ Multilayer on Germanium Nanocones Array with Light Trapping Effect for Sensitive Infrared Photodetector and Image Sensing Application Luo, Lin‐Bao; Wang, Di; Xie, Chao Advanced Functional Materials, Vol. 29, Issue 22 https://doi.org/10.1002/adfm.201900849	journal	March 2019
Multilayered PdSe ₂ /Perovskite Schottky Junction for Fast, Self‐Powered, Polarization‐Sensitive, Broadband Photodetectors, and Image Sensor Application Zeng, Long‐Hui; Chen, Qing‐Ming; Zhang, Zhi‐Xiang Advanced Science, Vol. 6, Issue 19 https://doi.org/10.1002/advs.201901134	journal	August 2019
Thickness-dependent charge transport in few-layer MoS ₂ field-effect transistors Lin, Ming-Wei; Kravchenko, Ivan I.; Fowlkes, Jason Nanotechnology, Vol. 27, Issue 16 https://doi.org/10.1088/0957-4484/27/16/165203	journal	March 2016
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712 https://doi.org/10.1038/nnano.2012.193	journal	November 2012
Pressure-induced superconductivity up to 13.1 K in the pyrite phase of palladium diselenide $PdS e_{2}$ ElGhazali, Moaz A.; Naumov, Pavel G.; Mirhosseini, Hossein Physical Review B, Vol. 96, Issue 6 https://doi.org/10.1103/PhysRevB.96.060509	journal	August 2017
Phase transitions in 2D materials Li, Wenbin; Qian, Xiaofeng; Li, Ju Nature Reviews Materials, Vol. 6, Issue 9 https://doi.org/10.1038/s41578-021-00304-0	journal	April 2021
Recent Progress on 2D Noble‐Transition‐Metal Dichalcogenides Pi, Lejing; Li, Liang; Liu, Kailang Advanced Functional Materials, Vol. 29, Issue 51 https://doi.org/10.1002/adfm.201904932	journal	October 2019
Anisotropic Electron-Photon and Electron-Phonon Interactions in Black Phosphorus Ling, Xi; Huang, Shengxi; Hasdeo, Eddwi H. Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.5b04540	journal	March 2016
Structural and quantum-state phase transitions in van der Waals layered materials Yang, Heejun; Kim, Sung Wng; Chhowalla, Manish Nature Physics, Vol. 13, Issue 10 https://doi.org/10.1038/nphys4188	journal	July 2017
Anomalous polarization dependence of Raman scattering and crystallographic orientation of black phosphorus Kim, Jungcheol; Lee, Jae-Ung; Lee, Jinhwan Nanoscale, Vol. 7, Issue 44 https://doi.org/10.1039/C5NR04349B	journal	January 2015
2D layered noble metal dichalcogenides (Pt, Pd, Se, S) for electronics and energy applications Chen, E.; Xu, W.; Chen, J. Materials Today Advances, Vol. 7 https://doi.org/10.1016/j.mtadv.2020.100076	journal	September 2020
Low-Frequency Interlayer Breathing Modes in Few-Layer Black Phosphorus Ling, Xi; Liang, Liangbo; Huang, Shengxi Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/acs.nanolett.5b01117	journal	May 2015
Van der Waals direction transformation induced by shear strain in layered PdSe2 Lv, Peng; Tang, Gang; Liu, Yanyu Extreme Mechanics Letters, Vol. 44 https://doi.org/10.1016/j.eml.2021.101231	journal	April 2021
Unusual Angular Dependence of the Raman Response in Black Phosphorus Ribeiro, Henrique B.; Pimenta, Marcos A.; de Matos, Christiano J. S. ACS Nano, Vol. 9, Issue 4 https://doi.org/10.1021/acsnano.5b00698	journal	February 2015
Layer-Dependent and In-Plane Anisotropic Properties of Low-Temperature Synthesized Few-Layer PdSe ₂ Single Crystals Lu, Li-Syuan; Chen, Guan-Hao; Cheng, Hui-Yu ACS Nano, Vol. 14, Issue 4 https://doi.org/10.1021/acsnano.0c01139	journal	April 2020
Recent advances in anisotropic two-dimensional materials and device applications Zhao, Jinlai; Ma, Dingtao; Wang, Cong Nano Research, Vol. 14, Issue 4 https://doi.org/10.1007/s12274-020-3018-z	journal	October 2020
The crystal structure of PdSe2 and PdS2 Grønvold, F.; Røst, E. Acta Crystallographica, Vol. 10, Issue 4 https://doi.org/10.1107/S0365110X57000948	journal	April 1957
Direct synthesis of metastable phases of 2D transition metal dichalcogenides Sokolikova, Maria S.; Mattevi, Cecilia Chemical Society Reviews, Vol. 49, Issue 12 https://doi.org/10.1039/D0CS00143K	journal	January 2020
Two-dimensional topological materials discovery by symmetry-indicator method Wang, Di; Tang, Feng; Ji, Jialin Physical Review B, Vol. 100, Issue 19 https://doi.org/10.1103/PhysRevB.100.195108	journal	November 2019
Controlled Synthesis of 2D Palladium Diselenide for Sensitive Photodetector Applications Zeng, Long-Hui; Wu, Di; Lin, Sheng-Huang Advanced Functional Materials, Vol. 29, Issue 1 https://doi.org/10.1002/adfm.201806878	journal	November 2018
Few-Layer PdSe ₂ Sheets: Promising Thermoelectric Materials Driven by High Valley Convergence Sun, Minglei; Chou, Jyh-Pin; Shi, Lihong ACS Omega, Vol. 3, Issue 6 https://doi.org/10.1021/acsomega.8b00485	journal	June 2018
Anisotropic Growth and Scanning Tunneling Microscopy Identification of Ultrathin Even‐Layered PdSe ₂ Ribbons Jiang, Shaolong; Xie, Chunyu; Gu, Yue Small, Vol. 15, Issue 45 https://doi.org/10.1002/smll.201902789	journal	September 2019
Exploring the air stability of PdSe2 via electrical transport measurements and defect calculations Hoffman, Anna N.; Gu, Yiyi; Liang, Liangbo npj 2D Materials and Applications, Vol. 3, Issue 1 https://doi.org/10.1038/s41699-019-0132-4	journal	December 2019
Phase-engineered low-resistance contacts for ultrathin MoS₂ transistors Kappera, Rajesh; Voiry, Damien; Yalcin, Sibel Ebru Nature Materials, Vol. 13, Issue 12, p. 1128-1134 https://doi.org/10.1038/nmat4080	journal	August 2014
New Verbeekite-type polymorphic phase and rich phase diagram in the PdSe2−xTex system Liu, Wenhao; Osanloo, Mehrdad Rostami; Wang, Xiqu Physical Review B, Vol. 104, Issue 2 https://doi.org/10.1103/PhysRevB.104.024507	journal	July 2021
Hopping transport through defect-induced localized states in molybdenum disulphide Qiu, Hao; Xu, Tao; Wang, Zilu Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3642	journal	October 2013
Defect-Mediated Phase Transformation in Anisotropic Two-Dimensional PdSe ₂ Crystals for Seamless Electrical Contacts Oyedele, Akinola D.; Yang, Shize; Feng, Tianli Journal of the American Chemical Society, Vol. 141, Issue 22 https://doi.org/10.1021/jacs.9b02593	journal	May 2019
Coplanar semiconductor–metal circuitry defined on few-layer MoTe2 via polymorphic heteroepitaxy Sung, Ji Ho; Heo, Hoseok; Si, Saerom Nature Nanotechnology, Vol. 12, Issue 11 https://doi.org/10.1038/nnano.2017.161	journal	September 2017
Two‐Dimensional Noble‐Metal Chalcogenides and Phosphochalcogenides Kempt, Roman; Kuc, Agnieszka; Heine, Thomas Angewandte Chemie International Edition, Vol. 59, Issue 24 https://doi.org/10.1002/anie.201914886	journal	April 2020
Highly Polarization-Sensitive, Broadband, Self-Powered Photodetector Based on Graphene/PdSe ₂ /Germanium Heterojunction Wu, Di; Guo, Jiawen; Du, Juan ACS Nano, Vol. 13, Issue 9 https://doi.org/10.1021/acsnano.9b03994	journal	July 2019
Electrical and Thermoelectric Transport by Variable Range Hopping in Thin Black Phosphorus Devices Choi, Seon Jae; Kim, Bum-Kyu; Lee, Tae-Ho Nano Letters, Vol. 16, Issue 7 https://doi.org/10.1021/acs.nanolett.5b04957	journal	June 2016
Quantum spin Hall state in monolayer 1T'-WTe2 Tang, Shujie; Zhang, Chaofan; Wong, Dillon Nature Physics, Vol. 13, Issue 7 https://doi.org/10.1038/nphys4174	journal	June 2017

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

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