Magnetic Stress-Driven Metal-Insulator Transition in Strongly Correlated Antiferromagnetic CrN.

Traditionally, the Coulomb repulsion or Peierls instability causes the metal-insulator phase transitions in strongly correlated quantum materials. In comparison, magnetic stress is predicted to drive the metal-insulator transition in materials exhibiting strong spin-lattice coupling. However, this mechanism lacks experimental validation and an in-depth understanding. Here we demonstrate the existence of the magnetic stress-driven metal-insulator transition in an archetypal material, chromium nitride. Structural, magnetic, electronic transport characterization, and first-principles modeling analysis show that the phase transition temperature in CrN is directly proportional to the strain-controlled anisotropic magnetic stress. The compressive strain increases the magnetic stress, leading to the much-coveted room-temperature transition. In contrast, tensile strain and the inclusion of nonmagnetic cations weaken the magnetic stress and reduce the transition temperature. This discovery of a new physical origin of metal-insulator phase transition that unifies spin, charge, and lattice degrees of freedom in correlated materials marks a new paradigm and could lead to novel device functionalities.

Functionalization of antimonene and bismuthene with Lewis acids.

Elemental 2D pnictogens (group 15) are an interesting class of materials with tunable band structures and high carrier mobilities. Heavier pnictogens (Sb and Bi) are stable under ambient conditions compared to lighter members (P and As) and are emerging as interesting candidates for various electronic and optoelectronic applications. The reactivity of these materials is due to the presence of a lone pair which can be effectively utilized to tune material properties via different functionalization strategies. In this work, we have synthesized antimonene and bismuthene nanosheets by liquid exfoliation which are emissive in the visible range and functionalized these nanosheets with group 12 and 13 Lewis acids (ZnCl2, CdCl2, BCl3, GaCl3, AlCl3, and InCl3). Interaction of these Lewis acids with the lone pairs on Sb/Bi leads to the formation of Lewis acid-base adducts with the corresponding changes in the bonding environment along with lattice distortion and rehybridization of the band structure. Interestingly, the changes in band structure upon functionalization were realized as a blue shift in the emission of few-layered Sb and Bi. This is the first report on the functionalization of heavier pnictogens by the formation of Lewis acid-base adducts and opens a path for tuning their properties for integration in electronic and optoelectronic devices.

Covalent Functionalization of Antimonene and Bismuthene Nanosheets.

Antimonene and bismuthene are promising members of the 2D pnictogen family with their tunable band gaps, high electronic conductivity, and ambient stability, making them suitable for electronic and optoelectronic applications. However, semi-metal to semiconductor transition occurs only in the mono/bilayer regime, limiting their applications. Covalent functionalization is a versatile method for tuning materials' chemical, electronic, and optical properties and can be explored for tuning the properties of pnictogens. In this work, emissions in liquid exfoliated antimonene and bismuthene are observed at ≈2.23 and ≈2.33 eV, respectively. Covalent functionalization of antimonene and bismuthene with p-nitrobenzene diazonium salt proceeds with the transfer of lone pairs from Sb/Bi to the diazonium salt, introducing organic moieties on the surface attached predominantly via Sb/BiC bonds. Consequently, Sb/Bi signatures in Raman and X-ray photoelectron spectra are blue-shifted, implying lattice distortion and charge transfer. Interestingly, emission can be tailored upon functionalization to 2.18 and 2.27 eV for antimonene and bismuthene respectively, and this opens the possibility of tuning the properties of pnictogens and related materials. This is the first report on covalent functionalization of antimonene and bismuthene. It sheds light on the reaction mechanism on pnictogen surfaces and demonstrates tunability of optical property and surface passivation.

Polar Semiconducting Scandium Nitride as an Infrared Plasmon and Phonon-Polaritonic Material.

The interaction of light with collective charge oscillations, called plasmon-polariton, and with polar lattice vibrations, called phonon-polariton, are essential for confining light at deep subwavelength dimensions and achieving strong resonances. Traditionally, doped-semiconductors and conducting metal oxides (CMO) are used to achieve plasmon-polaritons in the near-to-mid infrared (IR), while polar dielectrics are utilized for realizing phonon-polaritons in the long-wavelength IR (LWIR) spectral regions. However, demonstrating low-loss plasmon- and phonon-polaritons in one host material will make it attractive for practical applications. Here, we demonstrate high-quality tunable short-wavelength IR (SWIR) plasmon-polariton and LWIR phonon-polariton in complementary metal-oxide-semiconductor compatible group III-V polar semiconducting scandium nitride (ScN) thin films. We achieve both resonances by utilizing n-type (oxygen) and p-type (magnesium) doping in ScN that allows modulation of carrier concentration from 5 × 1018 to 1.6 × 1021 cm-3. Our work enables infrared nanophotonics with an epitaxial group III semiconducting nitride, opening the possibility for practical applications.