Direct observation of delithiation as the origin of analog memristance in LixNbO2

The discovery of analog LixNbO2 memristors revealed a promising new memristive mechanism wherein the diffusion of Li+ rather than O2- ions enables precise control of the resistive states. However, directly correlating lithium concentration with changes to the electronic structure in active layers remains a challenge and is required to truly understand the underlying physics. Chemically delithiated single crystals of LiNbO2 present a model system for correlating lithium variation with spectroscopic signatures from operando soft x-ray spectroscopy studies of device active layers. Using electronic structure modeling of the x-ray spectroscopy of LixNbO2 single crystals, we demonstrate that the intrinsic memristive behavior in LixNbO2 active layers results from field-induced degenerate p-type doping. We show that electrical operation of LixNbO2-based memristors is viable even at marginal Li deficiency and that the analog memristive switching occurs well before the system is fully metallic. This study serves as a benchmark for material synthesis and characterization of future LixNbO2-based memristor devices and suggests that valence change switching is a scalable alternative that circumvents the electroforming typically required for filamentary-based memristors

Interconversion of intrinsic defects in SrTiO3(001)SrTiO_3(001)

Photoemission features associated with states deep in the band gap of n−SrTiO₃ (001) are found to be ubiquitous in bulk crystals and epitaxial films. These features are present even when there is little signal near the Fermi level. Analysis reveals that these states are deep-level traps associated with defects. The commonly investigated defects—O vacancies, Sr vacancies, and aliovalent impurity cations on the Ti sites—cannot account for these features. Rather, ab initio modeling points to these states resulting from interstitial oxygen and its interaction with donor electrons

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi 0.8 Co 0.2− y Al y O 2 Cathodes

Abstract: Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2−yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes

Evidence of a second-order Peierls-driven metal-insulator transition in crystalline NbO2

The metal-insulator transition of NbO2 is thought to be important for the functioning of recent niobium oxide-based memristor devices, and is often described as a Mott transition in these contexts. However, the actual transition mechanism remains unclear, as current devices actually employ electroformed NbOx that may be inherently different to crystalline NbO2. We report on our synchrotron x-ray spectroscopy and density-functional-theory study of crystalline, epitaxial NbO2 thin films grown by pulsed laser deposition and molecular beam epitaxy across the metal-insulator transition at ~810⁰C. The observed spectral changes reveal a second-order Peierls transition driven by a weakening of Nb dimerization without significant electron correlations, further supported by our density-functional-theory modeling. Our findings indicate that employing crystalline NbO2 as an active layer in memristor devices may facilitate analog control of the resistivity, whereby Joule-heating can modulate Nb-Nb dimer distance and consequently control the opening of a pseudogap

Raman spectroscopy of lithium niobite (LiNbO2)

Lithium niobite (LiNbO2) single crystals fabricated via liquid phase electro-epitaxy are studied by Raman spectroscopy. We present the Raman spectra of the pristine and chemically delithiated LiNbO2 crystals under ambient conditions. Two characteristic experimental Raman peaks located at 456 cm−1 and 640 cm−1 are assigned to the O E2g and O A1g phonon modes respectively, as determined from first principles-based calculations. Furthermore, by chemically delithiating the crystals it is shown that the spectral changes of the O E2g can be used to capture lithium content variation within the structure

Direct Observation of Electrostatically Driven Band Gap Renormalization in a Degenerate Perovskite Transparent Conducting Oxide

We have directly measured the band gap renormalization associated with the Moss-Burstein shift in the perovskite transparent conducting oxide (TCO), La-doped BaSnO_{3}, using hard x-ray photoelectron spectroscopy. We determine that the band gap renormalization is almost entirely associated with the evolution of the conduction band. Our experimental results are supported by hybrid density functional theory supercell calculations. We determine that unlike conventional TCOs where interactions with the dopant orbitals are important, the band gap renormalization in La-BaSnO_{3} is driven purely by electrostatic interactions

Evolution of the Electrode–Electrolyte Interface of LiNi0.8Co0.15Al0.05O2\mathrm{LiNi_{0.8}Co_{0.15}Al_{0.05}O_{2}} Electrodes Due to Electrochemical and Thermal Stress

For layered oxide cathodes, impedance growth and capacity fade related to reactions at the cathode–electrolyte interface (CEI) are particularly prevalent at high voltage and high temperatures. At a minimum, the CEI layer consists of Li$_2$CO$_3$, LiF, reduced (relative to the bulk) metal-ion species, and salt decomposition species, but conflicting reports exist regarding their progression during (dis)charging. Utilizing transport measurements in combination with X-ray and nuclear magnetic resonance spectroscopy techniques, we study the evolution of these CEI species as a function of electrochemical and thermal stress for $\mathrm{LiNi_{0.8}Co_{0.15}Al_{0.05}O_{2}}$ (NCA) particle electrodes using a LiPF$_6$ ethylene carbonate:dimethyl carbonate (1:1 volume ratio) electrolyte. Although initial surface metal reduction does correlate with surface Li$_2$CO$_3$ and LiF, these species are found to decompose upon charging and are absent above 4.25 V. While there is trace LiPF$_6$ breakdown at room temperature above 4.25 V, thermal aggravation is found to strongly promote salt breakdown and contributes to surface degradation even at lower voltages (4.1 V). An interesting finding of our work was the partial reformation of LiF upon discharge, which warrants further consideration for understanding CEI stability during cycling