Polarization Switching on the Open Surfaces of the Wurtzite Ferroelectric Nitrides: Ferroelectric Subsystems and Electrochemical Reactivity

  • Yongtao Liu
  • , Anton V. Ievlev
  • , Eugene A. Eliseev
  • , Ali Mohammadi Dinani
  • , Alireza Sepehrinezhad
  • , Ubaidullah S. Hassan
  • , Drew Behrendt
  • , Nana Sun
  • , Kazuki Okamoto
  • , Hiroshi Funakubo
  • , Andrew M. Rappe
  • , Adri C.T. van Duin
  • , Anna N. Morozovska
  • , Sergei Kalinin

Research output: Contribution to journalArticlepeer-review

Abstract

Binary ferroelectric nitrides are promising materials for information technologies and power electronics. However, polarization switching in these materials is highly unusual. From the structural perspective, polarization reversal is associated with the change of the effective polarity at the surfaces and interfaces from N-to-M terminated, suggesting strong coupling between ferroelectric and chemical phenomena. Phenomenologically, macroscopic studies demonstrate the presence of complex time dependent phenomena including wake-up. Here, the polarization switching using the multidimensional high-resolution piezoresponse force microscopy (PFM) and spectroscopy is explored, detecting both the evolution of induced ferroelectric domain, electromechanical response, and surface deformation during first-order reversal curve measurements. The presence of two weakly coupled ferroelectric subsystems are demonstrated and the bias-induced electrochemical reactivity. The observed behaviors are very similar to the recent studies of other wurtzite system but additionally include electrochemical reactivity, suggesting the universality of these behaviors for the wurtzite binary ferroelectrics. These studies suggest potential of high-resolution multimodal PFM spectroscopies to resolve complex coupled polarization dynamics in materials. Furthermore, these PFM based studies are fully consistent with the recent electron microscopy observations of the shark-teeth like ferroelectric domains in nitrides. Hence, it is believed that these studies establish the universal phenomenological picture of polarization switching in binary wurtzite.

Original languageEnglish
JournalAdvanced Materials
DOIs
StateAccepted/In press - 2025

Funding

This effort (PFM and ToF‐SIMS experiments) was supported by the Center for Nanophase Materials Sciences (CNMS), which was a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory, and using instrumentation within ORNL's Materials Characterization Core provided by UT‐Battelle, LLC under Contract No. DE‐AC05‐00OR22725 with the U.S. Department of Energy. This research was sponsored by the INTERSECT Initiative as part of the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT‐Battelle, LLC for the US Department of Energy under contract DE‐AC05‐00OR22725. The work of E.A.E was funded by the National Research Foundation of Ukraine (project “Silicon‐compatible ferroelectric nanocomposites for electronics and sensors”, grant N 2023.03/0127). The work of A.N.M was funded by the National Research Foundation of Ukraine (project “Manyfold‐degenerated metastable states of spontaneous polarization in nanoferroics: theory, experiment and perspectives for digital nanoelectronics”, grant N 2023.03/0132). Obtained results were visualized in Mathematica 14.0. SVK effort was supported by the UT Knoxville start‐up funding. Film growth (H.F.) was supported by MEXT Program: Data Creation and Utilization Type Material Research and Development Project (No. JPMXP1122683430) and MEXT Initiative to Establish Next‐generation Novel Integrated Circuits Centers (X‐NICS) (JPJ011438), and the Japan Science and Technology Agency (JST) as part of Adopting Sustainable Partnerships for Innovative Research Ecosystem (ASPIRE), Grant Number JPMJAP2312. AMD, AS, ACTvD, U.S.H., D.B., and A.M.R. acknowledge funding for the ReaxFF and DFT modeling work from the center for 3D ferroelectric microelectronics (3DFeM2), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award Number DE‐SC0021118. Film growth (H.F.) was supported by MEXT program: Data Creation and Utilization Type Material Research and Development Project (JPMXP1122683430) and MEXT Initiative to Establish Next‐generation Novel Integrated Circuits Centers (X‐NICS) (JPJ011438), and the Japan Science and Technology Agency (JST) as part of Adopting Sustainable Partnerships for Innovative Research Ecosystem (ASPIRE), Grant Number JPMJAP2312, Adaptable and Seamless Technology transfer Program through Target‐driven R&D (A‐STEP) from Japan Science and Technology Agency (JST) Japan (JPMJTR24T4).

Keywords

  • Ferroelectrics
  • piezoresponse force microscopy
  • wurtzite

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