Photophysical characterization of 2,3-difunctionalized thieno[3,4-b]pyrazines

In order to better understand the optical properties of polythieno[3,4-b]pyrazine materials, the photophysical characteristics of a series of monomeric 2,3-difunctionalized thieno[3,4-b]pyrazines (where R=H, CH₃, C₆H₁₃, C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, and Ph) have been studied. Characterization of the room temperature UV-vis and fluorescence spectra, including solvent and pH dependence, are presented and compared to the related species isothianaphthene and quinoxaline.     

Fluorescence Properties and Dipole Moments of Novel Fused Thienobenzofurans. Solvent and Structural Effects

The electronic absorption, fluorescence excitation and emission spectra, and fluorescence quantum yields of novel fused thienobenzofurans, including thieno[3,2-b][1]benzofuran (1), [1]benzothieno[3,2-b]furan (2), and [1]benzothieno[3,2-b][1]benzofuran (3), were recorded in fourteen solvents of different polarities at room temperature. Compound 2 was not fluorescent. Experimental ground-state dipole moments of compounds 1–3 were measured in benzene at 298 K and compared with the corresponding theoretical dipole moment values. The solvent effects on the electronic absorption and fluorescence spectra of these thienobenzofurans were quantitatively investigated by means of solvatochromic correlations based on the Kawski-Chamma-Viallet and McRae equations. A weak negative solvatochromic behavior was found for these compounds, showing that their dipole moments are slightly lower in the excited singlet-state than in the ground-state. Kamlet-Abboud-Taft multiparameter relationships were also established for electronic absorption and fluorescence wavenumbers, and fluorescence quantum yields in most solvents, demonstrating the occurrence of specific solute-solvent interactions.     

Substituent Effect on Absorption and Fluorescence Properties of Thieno[3, 2-<Emphasis Type="Italic">c</Emphasis>]Pyridine Derivatives

New substituted thieno[3,2-c]pyridine derivatives 5 were synthesized by the reaction of 3-bromo-4-chlorothieno[3,2-c]pyridine 1 with cyclic amine 2, which further on Suzuki reaction with boronic acids 4 converted to corresponding 3-arylthieno[3,2-c]pyridine 5. Substituent R³ has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C₄ has no effect on fluorescence properties of thienopyridines.

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Graphical Abstract New thieno[3,2-c]pyridine derivatives were synthesized from 3-bromo-4-chlorothieno[3,2-c]pyridine and cyclic amines, which by on Suzuki reaction with boronic acids converted to corresponding 3-arylthieno[3,2-c]pyridine. Substituent R3 has predominant effect on fluorescence properties of thienopyridines. However, the electron donor amine at C4 has no effect on fluorescence properties of thienopyridines

     

Synthesis of Pyrazolopyridine Annulated Heterocycles and Study the Effect of Substituents on Photophysical Properties

Pyrazolo[3,4-b]pyridines having 4-chloro-5-chloroethyl side chain are synthesized by the reaction of 5-aminopyrazole and cyclic β-formylester gave aminopyrazolodihydrofuranone intermediate, which on cyclization in phosphorous oxychloride exclusively converted in to 4-chloro-5-chloroethyl pyrazolo[3,4-b]pyridines 4(a-b) in major amount. The side chain with acetic acid, thiourea and aromatic amines are used to form angular ring leads to formation of tricyclic Furo[2,3-d]pyrazolo[2,3-b]pyridines 5(a-b), pyrazolo[3,4-b]thieno[2,3-d]pyridines 6(a-b) and pyrazolo[3,4-b]pyrrolo[2,3-d]pyridines 7(a-n) respectively. The substituents effect at C₄ position on fluorescence properties of pyrazolopyridines has been studied. Moreover the effect of electron donor and halogen substituents on fluorescence properties of pyrazolopyrrolopyridines 7(a-n) has been investigated along with their fluorescent quantum yield.     

Bay capping via acetylene addition to polycyclic aromatic hydrocarbons: Mechanism and kinetics

The bay-capping mechanism on PAH armchair edges and the kinetics of acetylene addition to 6–6–5 and 5–6–5 bays have been explored by ab initio/RRKM-ME calculations. The bays on the edges were modeled by C₂₁H₁₁ and C₂₀H₉ radicals produced by H abstractions from 7H-benzo[c]cyclopenta[e]pyrene and dicyclopenta[cf]pyrene. The C₂₀H₉ + C₂H₂ reaction is shown to have a low entrance barrier and to rapidly form the capped product, indaceno[2,1,8,7-cdefg]pyrene, along with ethynyl substituted dicyclopenta[cf]pyrene at temperatures above 1400 K. The reactivity of C₂₁H₁₁ is shown to be governed by the location of the unpaired electron; the π radical R1 formed by H abstraction from the CH₂ group in 7H-benzo[c]cyclopenta[e]pyrene reacts with C₂H₂ very slowly owing to a high entrance barrier, with the bay-capping rate constant approaching 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ only at temperatures above 2000 K. This result reaffirms that the growth of π aryl radicals via acetylene addition is inefficient and reflects the generally low reactivity of such radicals where the spin density is highly delocalized over the entire polyaromatic system. Alternatively, the σ C₂₁H₁₁ radical R2 produced by H abstraction from the five-membered ring at the bay rapidly reacts with C₂H₂ forming the bay-capped product, with the rate constant on the order of 10⁻¹² cm³ molecule⁻¹ s⁻¹ at T ≥ 1500 K. Rate constants for the capping reactions at the 6–6–5 and 5–6–5 bays are compared with those at the 6–0–6, 6–6–6, and 6–5–6 bays. The site-specific bay-capping rate constants have been utilized in kMC simulations of the PAH growth and the results showed measurable differences when the 6–6–5 and 5–6–5 bay-capping reactions are taken into account, including an increase of the growth rate and the formation of closed-shell PAH and a rise of the number of embedded five-membered rings accompanied with a slight decrease of their overall amount.     

Cycloaddition of 2′-azidoethyl glycosides to fullerene[C60] under ultrasonic irradiation

The reactions of fullerene[C₆₀] with 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranoside (2a) and 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranoside (2b) under ultrasonic irradiation cause the cycloaddition of 2′-azidoethyl glycosides to fullerene[C₆₀] and lead to d-glycosyl fullerene[C₆₀] derivatives 3a and 3b, respectively. The glycosyl fullerene[C₆₀] derivatives were characterized by ¹H and ¹³C NMR, UV–vis, FAB-MS, FT-IR spectra and were a 1:1 glycoside fullerene [C₆₀]-adduct.     

Subnanosecond spectrofluorimetry of new indolocarbazole derivatives in solutions and protein complexes and their dipole moments

The spectral and temporal characteristics of new 6,12-dimethoxyindolo[3,2-b]carbazole, 5,11-dimethyl-6,12-dimethoxyindolo[3,2-b]carbazole, and 5,11-dihexyl-6,12-di(hexyloxy)indolo[3,2-b]carbazole fluorescence probes in organic solvents and protein complexes are studied. The dipole moments of indolocarbazoles in 1,4-dioxane were measured by electrooptical absorption method. The measured dipole moments have values within the range of (3.1–3.6) × 10⁻³⁰ C m in the equilibrium ground state and increase to (4.8–5.6) × 10⁻³⁰ C m after excitation. The excited state lifetime of indolocarbazole derivatives increases with increasing polarity and viscosity of the environment. The binding of indolocarbazoles with trypsinogen and human serum albumin increases the fluorescence intensity, changes the intensity ratio of fluorescence bands, and increases the average excited state lifetime of indolocarbazoles. The analysis of the instantaneous fluorescence spectra and fluorescence decay parameters at different wavelengths revealed the existence of several types of probe binding sites in proteins. It is found that the fluorescence characteristics of indolocarbazole derivatives depend on the conformation rearrangements of trypsinogen due to its thermal denaturation.     

2,7-Carbazole and thieno[3,4-c]pyrrole-4,6-dione based copolymers with deep highest occupied molecular orbital for photovoltaic cells

Three kinds of donor–acceptor (D–A) type photovoltaic polymers were synthesized based on 2,7-carbazole and thieno[3,4-c]pyrrole-4,6-dione (TPD). The conjugation of weakly electron (e)-donating 2,7-carbazole and strongly e-accepting TPD moieties yielded a deep highest occupied molecular orbital (HOMO) and its energy level was fine-controlled to be −5.72, −5.67 and −5.57 eV through the incorporation of thiophene (T), thieno[3,2-b]thiophene (TT) and bithiophene (BT) as a π-bridge. Polymer:[6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM) based bulk heterojunction solar cells exhibited a high open-circuit voltage (V_OC) in the range, 0.86–0.94 V, suggesting good agreement with the measured HOMO levels. Despite the high V_OC, the thiophene (or thienothiophene)-containing PCTTPD (or PCTTTPD) showed poor power conversion efficiency (PCE, 1.14 and 1.25%) because of the very low short-circuit current density (J_SC). The voltage-dependent photocurrent and photoluminescence quenching measurements suggested that hole transfer from PC₇₁BM to polymer depends strongly on the HOMO level of the polymer. The PCTTPD and PCTTTPD devices suffered from electron–hole recombination at the polymer/PC₇₁BM interfaces because of the insufficient energy offset between the HOMOs of the polymer and PC₇₁BM. The PCBTTPD:PC₇₁BM device showed the best PCE of 3.42% with a V_OC and J_SC of 0.86 V and 7.79 mA cm⁻², respectively. These results show that photovoltaic polymers should be designed carefully to have a deep HOMO level for a high V_OC and sufficient energy offset for ensuring efficient hole transfer from PC₇₁BM to the polymer.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

The effect of gamma irradiation on electrical and dielectric properties of Al-TiW-Pd2Si/n-Si Schottky diode at room temperature

The effects of ⁶⁰Co (γ-ray) irradiation on the electrical and dielectric properties of Al-TiW-Pd₂Si/n-Si Schottky diodes (SDs) have been investigated by using capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements at room temperature and 500 KHz. The corrected capacitance and conductance values were obtained by eliminating the effect of series resistance (R_s) on the measured capacitance (C_m) and conductance (G_m) values. The high-low frequency capacitance (CHF-CLF) method given in [12] as N_ss = (1/qA) [((1/C_LF) − (1/C_ox))⁻¹ −  ((1/C_HF) − (1/C_ox))⁻¹] was successfully adapted to the before-after irradiation capacitance given in this report as N_ss = (1/qA) [((1/C_bef) − (1/C_ox))⁻¹ − ((1/C_after) − (1/C_ox))⁻¹] for the analyzing the density of interface states. The N_ss-V plots give a distinct peak corresponding to localized interface states regions at metal and semiconductor interface. The experimental values of the ac electrical conductivity (σ_ac), the real (M′) and imaginary (M″) parts of the electrical modulus were found to be strong functions of radiation and applied bias voltage, especially in the depletion and accumulation regions. The changes in the dielectric properties in the depletion and accumulation regions stem especially from the restructuring and reordering of the charges at interface states and surface polarization whereas those in the accumulation region are caused by series resistance effect.     

Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts

Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li⁺/PEO) in one phase and for soft cations (Cu²⁺/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li⁺, Cu²⁺) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)₂-b-PEO-b-PEI-Cu(TFSI)₂ and PEI-Cu(TFSI)₂-b-PEO-LiTFSI-b-PEI-Cu(TFSI)₂. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)₂ with N/Cu²⁺ = 20:1 (10^− 6, respectively 2 × 10^− 4 S cm^− 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.     

Low-voltage-drive and high output current ZnO thin-film transistors with sputtering SiO2 as gate insulator

Low-voltage-drive ZnO thin-film transistors (TFTs) with room-temperature radio frequency magnetron sputtering SiO₂ as the gate insulator were fabricated successfully on the glass substrate. The ZnO-TFT operates in the enhancement mode with a threshold voltage of 4.2 V, a field effect mobility of 11.2 cm²/V s, an on/off ratio of 3.1 × 10⁶ and a subthreshold swing of 0.61 V/dec. The drain current can reach to 1 mA while the gate voltage is only of 12 V and drain voltage of 8 V. The C–V characteristics of a MOS capacitor with the structure of ITO/SiO₂/ZnO/Al was investigated. The carrier concentration N_D in the ZnO active layer was determined, the calculated N_D is 1.81 × 10¹⁶ cm⁻³, which is the typical value of undoped ZnO film used as the channel layer for ZnO-TFT devices. The experiment results show that SiO₂ film is a promising insulator for the low voltage and high drive capability oxide TFTs.     

Study of alkyl chain length dependent characteristics of imidazolium based ionic liquids [CnMIM]+[TFSA]− by Brillouin and dielectric loss spectroscopy

This study examined the acoustic phonon mode of ionic liquids consisting of 1-alkyl-3-methyl-imidazolium family (C_nMIM) cations with n values ranging from 2 to 10 and bis(trifluoromethylsulfonyl)amide (TFSA) anion in the temperature range from 300 K to 100 K. [C_nMIM]⁺[TFSA]^? showed depolarized (VH) components of Brillouin peaks at temperatures below the glass transition temperature when n is larger than 4. On the other hand, in the case of ionic liquids with different anions, such as [C₄MIM]⁺[BF₄]^?, [C₄MIM]⁺[PF₆]^? and [C₈MIM]⁺[BF₄]^?, the VH component of Brillouin peaks was not observed in the temperature range investigated. The dielectric loss spectra showed that the temperature dependence of alkyl chain domain relaxation of all ionic liquids followed the Arrhenius law and showed an increase in activation energy at the temperature where the VH component of Brillouin peak appeared. These results suggest that the observed depolarized component of Brillouin peak might originate from uniquely induced polarization in the 2nd domain composed of head groups of cations and anions.     

Electrical conductivity and dynamics of quasi-solidified lithium-ion conducting ionic liquid at oxide particle surfaces

Lithium ion conducting solid-state composites consisting of lithium ion conducting ionic liquid, lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) dissolved 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide (EMI-TFSA), denoted by [yMLi⁺][EMI⁺][TFSA⁻] in this study, and various oxide particles such as SiO₂, Al₂O₃, TiO₂ (anatase and rutile) and 3YSZ are synthesized via a liquid route for the molar concentration of lithium, y, to be 1. The composite consists of SiO₂ and the ionic liquid with y = 0.2 was also prepared. The ionic liquid are quasi-solidified at the above oxide particle surfaces when x is below 40 for y = 1 and x is below 30 for y = 0.2, corresponding to the confinable thickness of the ionic liquid at the oxides' surfaces to be approximately 5-10 nm regardless of the oxide compositions. The electrical conductivities of x vol.%[yMLi⁺][EMI⁺][TFSA^-]-SiO₂, Al₂O₃, TiO₂s or 3YSZ composites are evaluated by ac impedance measurements. The quasi-solid-state composites exhibited liquid-like high apparent conductivity, e.g. 10^− 3.3-10^− 2.0 S cm^− 1 in the temperature range of 323-538 K for SiO₂-ionic liquid composites with y = 1. The self-diffusion coefficients of the constituent species of x vol.% [yMLi⁺][EMI⁺][TFSA⁻] (x is below 40, y = 0.2 and 1) − SiO₂ are evaluated by the Pulse Gradient Spin Echo (PGSE)-NMR technique in the temperature range of 298-348 K. By the quasi-solidification of the ionic liquid at SiO₂ particle surfaces, the absolute values of the diffusion coefficients of all constituent species decreased. The SiO₂ surfaces work to promote ionization of ion pair, [EMI⁺][TFSA⁻], while significant influence on the solvation coordination, [Li(TFSA)_n + 1]ⁿ⁻, was not observed. The apparent transport numbers of Li-containing species both in the bulk and the quasi-solidified ionic liquid showed similar values with each other, which was evaluated to be in the range of 0.010-0.017 for y = 0.2 and 0.051-0.093 for y = 1 in the abovementioned temperature range.     

Optical Properties of Solid Pseudoisocyanine Films Doped with Cluster Derivatives of Boron Hydrides

The formation and optical properties of J aggregates of pseudoisocyanine iodide in solid films in the presence of cluster anionic derivatives of boron hydrides and carboranes (B₁₀H ₁₀ ^2- , B₁₂H ₁₂ ^2- , B₂₀H ₁₈ ^2- , [Ni^IV(1,2-B₉C₂H₁₁)₂]⁰, 1,2-B₉C₂H ₁₂ ^- , [Co(1,2-B₉C₂H₁₁)₂]^-, [Ni(1,2-B₉C₂H₁₁)₂]^-, B₁₀H₈I ₂ ^2- , [Sn(1,2-B₉C₂H₁₁)]⁰) are studied. It is shown that the addition of anions B₁₀H ₁₀ ^2- or B₁₀H₈I ₂ ^2- leads to an efficient formation of stable J aggregates. The addition of carborane complex of nickel [Ni^IV (1,2-B₉C₂H₁₁)₂]⁰ also leads to the formation of J aggregates, although less stable ones. Carborane complex of tin [Sn^II(1,2-B₉C₂H₁₁)]⁰ facilitates the formation of a monomeric form of the dye. The remaining compounds yield no distinct pattern of formation of a certain monomeric or J-aggregated film structure. With the aid of the semiempirical AM1 method, the charge distributions in the cation of the dye and anionic derivatives of the boron hydrides are calculated. It is supposed that the bipolar distribution of a negative charge in the B₁₀H ₁₀ ^2- anion facilitates the formation of a J aggregate. By addition of salts of organic cations to a film of pseudoisocyanine-closo-hydrodecaborate (PCG), J aggregates with a narrow width of the J peak are obtained. The thermal decay of J aggregates in these films is studied. On the basis of the data obtained (the presence of an isosbestic point upon thermal decomposition of J aggregates and their reaggregation; the narrowing and increasing of the J absorption peak, as well as increasing of luminescence, upon dilution of a J-aggregated PCG film with organic cations; and the bipolar character of the electrostatic interaction of the B₁₀H ₁₀ ^2- anion with the dye), it is assumed that the J peak of pseudoisocyanine in the films studied corresponds to the absorption of a dimeric form of the dye.     

Top-gate amorphous IGZO thin-film transistors with a SiO buffer layer inserted between active channel layer and gate insulator

In this paper, top-gate thin-film transistors (TFTs) using amorphous In-Ga-Zn-O as the n-channel active layer and SiO₂ as gate insulator were fabricated by radio frequency magnetron sputtering at room temperature. In this device, a SiO layer was used to be a buffer layer between active layer and gate insulator for preventing the damage of the InGaZnO surface by the process of sputtering SiO₂ with relatively high sputtering power. The thickness of buffer layers was studied and optimized for enhancing the TFTs performances. Contrasting to the TFTs without buffer layer, the optimized thickness of 10 nm SiO buffer layer improved the top-gate TFTs performances greatly: mobility increases 30%, reached 1.29 cm²/V s, the I_on/I_off ratio increases 3 orders, and the trap density at the interface of channel/insulator decreases about 1 order, indicated that the improvement of semiconductor/dielectric interface by buffering the sputtering power.     

Optical and electrical properties of Ge-implanted SiO2 layers on n-Si and p-Si

Ge ions of 100 keV were implanted into a 120 nm-thick SiO₂ layer on n-Si at room temperature while those of 80 keV were into the same SiO₂ layer on p-Si. Samples were, subsequently, annealed at 500°C for 2 h to effectively induce radiative defects in the SiO₂. Maximum intensities of sharp violet photoluminescence (PL) from the SiO₂/n-Si and the SiO₂/p-Si samples were observed when the samples have been implanted with doses of 1×10¹⁶ and 5×10¹⁵ cm⁻², respectively. According to current–voltage (I–V) characteristics, the defect-related samples exhibit large leakage currents with electroluminescence (EL) at only reverse bias region regardless of the type of substrate. Nanocrystal-related samples obtained by an annealing at 1100°C for 4 h show the leakage at both the reverse and the forward region.     

Red organic light-emitting diodes with high efficiency,low driving voltage and saturated red color realized via two step energy transfer based on ADN and Alq3 co-host system

We demonstrated efficient red organic light-emitting diodes based on a wide band gap material 9,10-bis(2-naphthyl)anthracene (ADN) doped with 4-(dicyano-methylene)-2-t-butyle-6-(1,1,7,7-tetramethyl-julolidyl-9-enyl)-4H-pyran (DCJTB) as a red dopant and 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10(2-benzothiazolyl)quinolizine-[9,9a,1gh]coumarin (C545T) as an assistant dopant. The typical device structure was glass substrate/ITO/4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)triphenylamine (m-MTDATA)/N,N′-bis(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB)/[ADN:Alq₃]:DCJTB:C545T/Alq₃/LiF/Al. It was found that C545T dopant did not by itself emit but did assist the energy transfer from the host (ADN) to the red emitting dopant via cascade energy transfer mechanism. The OLEDs realized by this approach significantly improved the EL efficiency. We achieved a significant improvement regarding saturated red color when a polar co-host emitter (Alq₃) was incorporated in the matrix of [ADN:Alq₃]. Since ADN possesses a considerable high electron mobility of 3.1 × 10⁻⁴ cm²  V⁻¹ s⁻¹, co-host devices with high concentration of ADN (>70%) exhibited low driving voltage and high current efficiency as compared to the devices without ADN. We obtained a device with a current efficiency of 3.6 cd/A, Commission International d’Eclairage coordinates of [0.618, 0.373] and peak λ_max = 620 nm at a current density of 20 mA/cm². This is a promising way of utilizing wide band gap material as the host to make red OLEDs, which will be useful in improving the electroluminescent performance of devices and simplifying the process of fabricating full color OLEDs.     

DFT(B3LYP/LanL2DZ), non-linear optical and electrical studies of a new hybrid compound: [C6H10(NH3)2]CoCl4·H2O

A new organic-inorganic material [C₆H₁₀(NH₃)₂]CoCl₄·H₂O was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, thermal analysis and dielectric technique. It crystallizes in the non-centrosymmetric space group Pna2₁ with the following unit cell parameters: a=12.5328(1) Å, b=9.0908(1) Å, c=11.7440(1) and α=β=γ=90°. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated H₂O, isolated [CoCl₄]²⁻ tetrahedral anions and diammoniumcyclohexane [C₆H₁₀(NH₃)₂]²⁺ cations, which are connected via N–H…Cl, N–H…O and O–H…N hydrogen bonds. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. Theoretical calculations were performed using DFT/B3LYP/LanL2DZ method for studying the molecular structure and vibrational spectra and especially to examine the non-linear optical behavior of the compound. Solid state ¹³C NMR spectrum shows three signals correspond to three different carbon environments. Thermal analysis discloses a phase transition at the temperature 315 K and the evaporation of water molecule at 327 K. A detailed dielectric study was reported and shows a good agreement with thermal measurements.     

The effect of interface states, excess capacitance and series resistance in the Al/SiO2/p-Si Schottky diodes

The current-voltage (I-V) characteristics of Al/SiO₂/p-Si metal-insulator-semiconductor (MIS) Schottky diodes were measured at room temperature. In addition the capacitance-voltage (C-V) and conductance-voltage (G-V) measurements are studied at frequency range of 10 kHz-1 MHz. The higher value of ideality factor of 3.25 was attributed to the presence of an interfacial insulator layer between metal and semiconductor and the high density of interface states localized at Si/SiO₂ interface. The density of interface states (N_ss) distribution profile as a function of (E_ss − E_v) was extracted from the forward bias I-V measurements by taking into account the bias dependence of the effective barrier height (Φ_e) at room temperature for the Schottky diode on the order of ≅4 × 10¹³ eV⁻¹ cm⁻²_. These high values of N_ss were responsible for the non-ideal behaviour of I-V and C-V characteristics. Frequency dispersion in C-V and G-V can be interpreted only in terms of interface states. The N_ss can follow the ac signal especially at low frequencies and yield an excess capacitance. Experimental results show that the I-V, C-V and G-V characteristics of SD are affected not only in N_ss but also in series resistance (R_s), and the location of N_ss and R_s has a significant on electrical characteristics of Schottky diodes.