Synthesis and crystal structures of Ni(II), Cu(II) and μ-oxo-Fe(III) complexes of a salen type ligand: Mononuclear versus multinuclear complex formation

The nickel, copper and iron complexes of bis(salicylidene)-meso-1,2-diphenylethylendiaminato (mdpSal^2?) and their propensity to form multinuclear complexes similar to those observed for Co(mdpSal) are reported. The syntheses of the primary compounds were carried out with M(OAc)₂·xH₂O (M = Fe, Ni or Cu) and mdpSalH₂ in methanol. The Ni and Cu reactions resulted in the isolation of mononuclear Ni(mdpSal) (1) and Cu(mdpSal) (2) complexes. Both species 1 and 2 adopt approximate square planar geometries in the monoclinic space group P2₁/n and are iso-structural to the previously reported Co(mdpSal). Although structurally similar, neither 1 nor 2 exhibit comparable reactivity as reported for the cobalt analogue of mdpSal^?2 in forming multinuclear complexes. The iron reaction yielded a μ-oxo species [Fe(mdpSal)]₂O (3) in which each iron center is oxidized to +3 and ligated to one mdpSal^2? ligand frame with each iron center adopting distorted square pyramid geometry. In addition, Co(Salophen) (4) (SalophenH₂ = N,N′-bis(salicylidene)-1,2-phenylenediamine) has been synthesized and its reactivity assessed and compared to Co(mdpSal). Complexes 1–3 have been characterized by X-ray crystallography as well as UV–Vis and IR spectroscopy. A detailed comparison of the structural and spectral characteristics of the iso-structural complexes 1 and 2 with Co(mdpSal) are presented along with a discussion of factors that contributed to the unique reactivity observed for [Co(mdpSal)].     

Photoluminescence analyses of hydrogenated amorphous silicon nitride thin films

Silicon-rich hydrogenated amorphous silicon nitride (a-SiN_x:H) films were grown by plasma enhanced chemical vapor deposition (PECVD) with different r=NH₃/SiH₄ gas flow ratios. The optical absorption characteristics were analyzed by Fourier transform infrared (FTIR) and UV-visible transmittance spectroscopies. The recombination properties were investigated via photoluminescence (PL) measurements. As r was increased from 2 to 9, the PL emission color could be adjusted from red to blue with the emission intensity high enough to be perceived by naked eye at room temperature. The behaviors of the PL peak energy and the PL band broadness with respect to the optical constants were discussed in the frame of electron-phonon coupling and band tail recombination models. A semiquantitative analysis supported the band tail recombination model, where the recombination was found to be favored when the carriers thermalize to an energy level at which the band tail density of states (DOS) reduces to some fraction of the relevant band edge DOS. For the PL efficiency comparison of the samples with different nitrogen contents, the PL intensity was corrected for the absorbed intensity fraction of the incident PL excitation source. The resulted correlation between the PL efficiency and the subgap absorption tail width further supported the band tail recombination model.     

Low temperature plasma production of hydrogenated nanocrystalline silicon thin films

The hydrogenated nanocrystalline silicon (nc-Si:H) thin films were produced by capacitively-coupled plasma enhanced chemical vapor deposition (PECVD) technique at low substrate temperatures (T_s ≈ 40–200 °C). Firstly, for particular growth parameters, the lowest stable T_s was determined to avoid temperature fluctuations during the film deposition. The influence of the T_s on the structural and optical properties of the films was investigated by the Fourier transform infrared (FTIR), UV–visible transmittance/reflectance and X-ray diffraction (XRD) spectroscopies. Also, the films deposited at the center of the PECVD electrode and those around the edge of the PECVD electrode were compared within each deposition cycle. The XRD and UV–visible reflectance analyses reveal the nanocrystalline phase for the films grown at the edge at all T_s and for the center films only at 200 °C. The crystallinity fraction and lateral dark conductivity decrease with lowered T_s. FTIR analyses were used to track the hydrogen content, void fraction and amorphous matrix volume fraction within the films. The optical constants obtained from the UV–visible transmittance spectroscopy were correlated well with the FTIR results. Finally, the optimal T_s was concluded for the application of the produced nc-Si:H in silicon-based thin film devices on plastic substrates.     

Electroforming of thin film silicon based homojunction pin diode

The recent observations of bright visible electroluminescence (EL) from electroformed thin film silicon based wide-gap alloys are further clamped down in a simpler structure. For this purpose, a standard quality, ordinary hydrogenated amorphous silicon (a-Si:H) homojunction pin diode was fabricated by plasma enhanced chemical vapor deposition. The fresh diode was characterized by temperature scanned current–voltage (I–V) and constant photocurrent measurements. The energy distribution of density of states within the forbidden gap of the intrinsic a-Si:H layer was determined by space charge limited current and optical absorption spectroscopies. Then the diode was intentionally subjected to a sufficiently high, calibrated electric field leading to its Joule heating assisted rapid crystallization at ambient atmosphere. The fresh and the formed diodes exhibit different I–V and EL characteristics. The current density of the formed diode increases drastically at low voltages while remaining unchanged at high voltages when compared to that of the fresh diode. Parallelly, the room temperature EL intensity under a particular current stress is boosted with electroforming. These interesting phenomena have been discussed in the frame of a self-consistent model.     

Electrical transport mechanism in boron nitride thin film

Both dc and ac transport characteristics of plasma enhanced chemical vapor deposited (PECVD) boron nitride (BN) thin film was investigated by dc current vs. dc voltage measurement at different temperatures and admittance vs. gate voltage at various frequencies/temperatures, respectively. MIM ≡ metal (Al)-insulator (BN)-metal (Al) or MIS ≡ metal (Al)-BN-semiconductor (p-Silicon) test devices were conventionally produced. Both conductivity anisotropy and dc/ac detailed transport mechanism were analyzed within the frame of a turbostratic structure (t-BN), interfacing the substrate by a thin amorphous layer (a-BN). This defective BN film has been justified by both infrared (IR) analysis and indirectly by the resulting electrical transport behavior. Transport and its variations as a function of temperature/frequency are in agreement with a hopping mechanism across Gauss-like energy distributed localized deep traps.     

Influence of the nitrogen flow rate on the order and structure of PECVD boron nitride thin films

Three sets of boron nitride (BN) thin films are deposited with different N₂/B₂H₆ flow ratios (r = 4, 10 and 25) by plasma enhanced chemical vapor deposition (PECVD). The variations of physical properties in different deposition sets are analyzed by optical (XPS, FTIR, UV–visible spectroscopies), mechanical and electrical measurements. The films are considered to be deposited in a turbostratic phase (t-BN). Evolution of bonding configurations with increasing r is discussed. Relatively higher nitrogen flow rate in the source gas mixture results in lower deposition rates, whereas more ordered films, which tend to reach a unique virtual crystal of band gap 5.93 eV, are formed. Anisotropy in the film structure and film inhomogeneity along the PECVD electrode radial direction are investigated.     

One more type of extrathermodynamic relationship

A new type of extrathermodynamic relationship is presented: DeltaH = Ti[DeltaS + R Delta(ln Omega)] + beta, where Omega is the phase volume and beta is a constant. This type of relationship holds for a series of systems in the case where deltaDelta(ln Omega) is changeable. The relation between this type of correlation and linear free-energy relationships is shown. An example of the specified correlation for energy parameters of excimers forming in different dipyrenylalkanes is demonstrated.     

Transport and luminescence phenomena in electroformed silicon nitride-based light emitting diode

Abstract

Hydrogenated amorphous silicon nitride-based heterojunction pin diode was electroformed under sufficiently high forward bias stress leading to its instant nanocrystallization at room temperature. In order to investigate the origin of the accompanying bright visible light emission, current-voltage and electroluminescence (EL) characteristics of the electroformed diode were scanned over temperature. Electrical transport mechanism was analysed in the low, medium and high electric field regimes. Temperature and field dependence of thermal activation energy were discussed. EL characteristics were studied using the spectral energy distribution and the injection current dependence of its intensity. Thermal quenching data of EL and photoluminescence intensities were compared. Finally, the relationship between the electrical transport and luminescence phenomena was attempted to be interpreted within the frame of a self-consistent model.     

Regioselective Synthesis of Fused Azo‐linked Pyrazolo[4,3‐e]pyridines Using Nano‐Fe3O4

A multicomponent reaction for the synthesis of fused azo‐linked pyrazolo[4,3‐e]pyridines from 3‐amino‐5‐methylpyrazole, indan‐1,3‐dione and synthesized azo‐linked aldehydes using nano‐Fe₃O₄ as an effective and reusable catalyst is reported. The present methodology offers several advantages, such as a simple procedure with an easy work‐up, short reaction times, high yields, and the absence of any volatile and hazardous organic solvents.