Understanding the Seebeck coefficient of LaNiO3 compound in the temperature range 300-620 K

Transition metal oxides have been attracted much attention in thermoelectric community from the last few decades. In the present work, we have synthesized LaNiO3 by a simple solution combustion process. To analyze the crystal structure and structural parameters we have used Rietveld refinement method wherein FullProf software is employed. The room temperature x-ray diffraction indicates the rhombohedral structure with space group R 3 c (No. 167). The refined values of lattice parameters are a = b = c = 5.4071 Å. Temperature dependent Seebeck coefficient (S) of this compound has been investigated by using experimental and computational tools. The measurement of S is conducted in the temperature range 300-620 K. The measured values of S in the entire temperature range have negative sign that indicates n-type character of the compound. The value of S is found to be ∼ -8 µV/K at 300 K and at 620 K this value is ∼ -12 µV/K. The electronic structure calculation is carried out using DFT+U method due to having strong correlation in LaNiO3. The calculation predicts the metallic ground state of the compound. Temperature dependent S is calculated using BoltzTraP package and compared with experiment. The best matching between experimental and calculated values of S is observed when self-interaction correction is employed as double counting correction in spin-polarized DFT + U (= 1 eV) calculation. Based on the computational results maximum power factors are also calculated for p-type and n-type doping of this compound.

Half Metallic Ferromagnetism and Transport Properties of Zinc Chalcogenides ZnX2Se4 (X = Ti, V, Cr) for Spintronic Applications

In ferromagnetic semiconductors, the coupling of magnetic ordering with semiconductor character accelerates the quantum computing. The structural stability, Curie temperature (Tc), spin polarization, half magnetic ferromagnetism and transport properties of ZnX2Se4 (X = Ti, V, Cr) chalcogenides for spintronic and thermoelectric applications are studied here by density functional theory (DFT). The highest value of Tc is perceived for ZnCr2Se4. The band structures in both spin channels confirmed half metallic ferromagnetic behavior, which is approved by integer magnetic moments (2, 3, 4) μB of Ti, V and Cr based spinels. The HM behavior is further measured by computing crystal field energy ΔEcrystal, exchange energies Δx(d), Δx (pd) and exchange constants (Noα and Noβ). The thermoelectric properties are addressed in terms of electrical conductivity, thermal conductivity, Seebeck coefficient and power factor in within a temperature range 0–400 K. The positive Seebeck coefficient shows p-type character and the PF is highest for ZnTi2Se4 (1.2 × 1011 W/mK2) among studied compounds.

Doping limits in p-type oxide semiconductors

The ability to dope a semiconductor depends on whether the Fermi level can be moved into its valence or conduction bands, on an energy scale referred to the vacuum level. For oxides, there are various suitable n-type oxide semiconductors, but there is a marked absence of similarly suitable p-type oxides. This problem is of interest not only for thin-film transistors for displays, or solar cell electrodes, but also for back-end-of-line devices for the semiconductor industry. This has led to a wide-ranging search for p-type oxides using high-throughput calculations. We note that some proposed p-type metal oxides have cation s-like lone pair states. The defect energies of some of these oxides were calculated in detail. The example SnTa2O6 is of interest, but others have structures more closely based on perovskite structure and are found to have more n-type than p-type character. Graphic abstract

Charged Forms of 2,6-Dinitro-1-oxidopyridin-1-ium-3,5-diamine - A DFT Treatment

The titled structure possesses many electron donating and attracting groups and should have push-pull type character. Its constitutional isomer, 2,6-diamino-3,5-dinitropyridine-N-oxide is a heat-resistant explosive material. In the present article, the charged forms of the titled structure have been investigated within the constraints of density functional theory at the level of UB3LYP/6-31++G(d,p). The calculations have revealed that it is electronically less stable than its isomer, 2,6-diamino-2,5-dinitropyridine-N-oxide. Some structural, electronic, quantum chemical and spectral behavior of ±1, ±2 type ions of it are considered presently.

Photoluminescence of Ni(II), Pd(II), and Pt(II) Complexes [M(Me2dpb)Cl] Obtained from C‒H Activation of 1,5-Di(2-pyridyl)-2,4-dimethylbenzene (Me2dpbH)

The three complexes [M(Me2dpb)Cl] (M = Ni, Pd, Pt) containing the tridentate N,C,N-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Me2dpb−) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along the series Pt < Ni < Pd from 0.15 to 0.74 V. DFT calculations confirmed the essentially ligand-centred π*-type character of the lowest unoccupied molecular orbital (LUMO) for all three complexes in agreement with the invariant reduction processes. For the highest occupied molecular orbitals (HOMO), contributions from metal dyz, phenyl C4, C2, C1, and C6, and Cl pz orbitals were found. As expected, the dz2 (HOMO-1 for Ni) is stabilised for the Pd and Pt derivatives, while the antibonding dx2−y2 orbital is de-stabilised for Pt and Pd compared with Ni. The long-wavelength UV-vis absorption band energies increase along the series Ni < Pt < Pd. The lowest-energy TD-DFT-calculated state for the Ni complex has a pronounced dz2-type contribution to the overall metal-to-ligand charge transfer (MLCT) character. For Pt and Pd, the dz2 orbital is energetically not available and a strongly mixed Cl-to-π*/phenyl-to-π*/M(dyz)-to-π* (XLCT/ILCT/MLCT) character is found. The complex [Pd(Me2dpb)Cl] showed a structured emission band in a frozen glassy matrix at 77 K, peaking at 468 nm with a quantum yield of almost unity as observed for the previously reported Pt derivative. No emission was observed from the Ni complex at 77 or 298 K. The TD-DFT-calculated states using the TPSSh functional were in excellent agreement with the observed absorption energies and also clearly assessed the nature of the so-called “dark”, i.e., d‒d*, excited configurations to lie low for the Ni complex (≥3.18 eV), promoting rapid radiationless relaxation. For the Pd(II) and Pt(II) derivatives, the “dark” states are markedly higher in energy with ≥4.41 eV (Pd) and ≥4.86 eV (Pt), which is in perfect agreement with the similar photophysical behaviour of the two complexes at low temperatures.

Enhanced Electrical Performance of Monolayer MoS2 with Rare Earth Element Sm Doping

Rare earth (RE) element-doped two-dimensional (2D) transition metal dichalcogenides (TMDCs) with applications in luminescence and magnetics have received considerable attention in recent years. To date, the effect of RE element doping on the electronic properties of monolayer 2D-TMDCs remains unanswered due to challenges including the difficulty of achieving valid monolayer doping and introducing RE elements with distinct valence and atomic configurations. Herein, we report a unique strategy to grow the Sm-doped monolayer MoS2 film by using an atmospheric pressure chemical vapor deposition method with the substrate face down on top of the growth source. A stable monolayer triangular Sm-doped MoS2 was achieved. The threshold voltage of an Sm-doped MoS2-based field effect transistor (FET) moved from −12 to 0 V due to the p-type character impurity state introduced by Sm ions in monolayer MoS2. Additionally, the electrical performance of the monolayer MoS2-based FET was improved by RE element Sm doping, including a 500% increase of the on/off current ratio and a 40% increase of the FET’s mobility. The electronic property enhancement resulted from Sm doping MoS2, which led internal lattice strain and changes in Fermi energy levels. These findings provide a general approach to synthesize RE element-doped monolayer 2D-TMDCs and to enrich their applications in electrical devices.