Tatyana Kravchuk

The incorporation of organic self‐assembled monolayers (SAMs) in microelectronic devices requires precise spatial control over the self‐assembly process. In this work, selective deposition of N‐heterocyclic carbenes (NHCs) on specific electrodes within a two‐microelectrode array is achieved by using pulsed electrodeposition. Spectroscopic analysis of the NHC‐coated electrode arrays reveals that each electrode is selectively coated with a designated NHC. The impact of NHC monolayers on the electrodes’ work function is quantified using Kelvin probe force microscopy. These measurements demonstrate that the work function values of each electrode can be independently tuned by the adsorption of a specific NHC. The presented deposition method enables to selectively coat designated microelectrodes in an electrode array with chosen NHC monolayers for tuning their chemical and electronic functionality.

In this work, we continued our systematic investigations on synthesis, structural studies, and electrochemical behavior of Ni-rich materials Li[Ni_xCo_yMn_z]O₂ (x + y + z = 1; x ≥ 0.8) for advanced lithium-ion batteries (LIBs). We focused, herein, on LiNi_0.85Co_0.10Mn_0.05O₂ (NCM85) and demonstrated that doping this material with high-charge cation Mo⁶⁺ (1 at. %, by a minor nickel substitution) results in substantially stable cycling performance, increased rate capability, lowering of the voltage hysteresis, and impedance in Li-cells with EC-EMC/LiPF₆ solutions. Incorporation of Mo-dopant into the NCM85 structure was carried out by in-situ approach, upon the synthesis using ammonium molybdate as the precursor. From X-ray diffraction studies and based on our previous investigation of Mo-doped NCM523 and Ni-rich NCM811 materials, it was revealed that Mo⁶⁺ preferably substitutes Ni residing either in 3a or 3b sites. We correlated the improved behavior of the doped NCM85 electrode materials in Li-cells with a partial Mo segregation at the surface and at the grain boundaries, a tendency established previously in our lab for the other members of the Li[Ni_xCo_yMn_z]O₂ family.

Doping Ni-rich LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode material by small amount of Mo6+ ions, around 1 mol.%, affects pronouncedly its structure, surface properties, electronic and electrochemical behavior. Cathodes comprising Mo6+ doped NCM523 exhibited in Li cells higher specific capacities, higher rate capabilities, lower capacity fading and lower charge-transfer resistance that relates to a more stable electrode/solution interface due to doping. This, in turn, is ascribed to the fact that the Mo6+ ions tend to concentrate more at the surface, as a result of a synthesis that always includes a necessary calcination - high temperature stage. This phenomenon of the Mo-dopant segregation at the surface in NCM523 material was discovered in the present work for the first time. It appears that Mo-doping reduces the reactivity of the Ni rich NCM cathode materials towards the standard electrolyte solutions of Li-ion batteries. Using density functional theory (DFT) calculations we showed that Mo6+ ions are preferably incorporated at Ni sites, and that the doping increases the amount of Ni2+ ions at the expense of Ni3+ ions, due to charge compensation, in accord with X-ray absorption fine-structure (XAFS) spectroscopy measurements. Further, DFT calculations predicted NiO bond length distributions in good agreement with the XAFS results, supporting a model of partial substitution of Ni sites by Molybdenum.

We followed the collective atomic-scale motion of Na atoms on a vicinal Cu(115) surface within a time scale of pico- to nanoseconds using helium spin echo spectroscopy. The well-defined stepped structure of Cu(115) allows us to study the effect that atomic steps have on the adsorption properties, the rate for motion parallel and perpendicular to the step edge, and the interaction between the Na atoms. With the support of a molecular dynamics simulation we show that the Na atoms perform strongly anisotropic 1D hopping motion parallel to the step edges. Furthermore, we observe that the spatial and temporal correlations between the Na atoms that lead to collective motion are also anisotropic, suggesting the steps efficiently screen the lateral interaction between Na atoms residing on different terraces.

We have investigated ethene and oxygen co-adsorption on Cu(410) by high resolution electron energy loss spectroscopy. We find that these two species compete for the adsorption sites and that pre-exposure to oxygen affects ethene adsorption more or less strongly depending on oxygen coverage and the kind of occupied sites. The c(2 × 2) O overlayer is inert with respect to ethene adsorption, while when some oxygen is removed by thermally induced subsurface incorporation, ethene chemisorption is restored. The latter species also adsorbs on the disordered oxygen phase formed when O(2) is dosed at low crystal temperature. Contrary to the bare surface case, most of the ethene ends up in a π-bonded configuration. Dehydrogenation occurs, too, albeit as a minority channel. The so-produced carbon reacts already at low temperature with adsorbed oxygen to yield carbon monoxide, which desorbs around 190 K.