Synthesis,characterization and electrochemical properties of novel metal free and zinc(II) phthalocyanines of ball and clamshell types

The phthalodinitrile derivative 1 was prepared by the reaction of 4-nitrophthalonitrile and 1,3-dimethoxy-4-tert-butylcalix[4]arene in dry dimethylsulfoxide as the solvent, in the presence of the base K₂CO₃, by nucleophilic substitution of an activated nitro group in an aromatic ring. The tetramerization of compound 1 gave a binuclear zinc(II) phthalocyanine and a metal-free phthalocyanine of the ball type, 2 and 3, respectively. Its condensation with 4,5-bis(hexylthio)phthalonitrile results in a binuclear phthalocyanine of the clamshell type, 4. The newly synthesized compounds were characterized by elemental analysis, UV–Vis, IR, MS and ¹H NMR spectra. The electronic spectra exhibit an intense π → π^∗ transition with characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of 2–4 were examined by cyclic voltammetry in non-aqueous media. The voltammetric results showed that while there is no considerable interaction between the two phthalocyanine rings in 4, the splitting of a molecular orbital occurs as a result of the strong interaction between the phthalocyanine rings in 2 and 3.     

The effect of PVA (Bi2O3-doped) interfacial layer and series resistance on electrical characteristics of Au/n-Si (110) Schottky barrier diodes (SBDs)

Two types of Schottky Barrier Diodes (SBDs) with and without PVA (Bi₂O₃-doped) polymeric interfacial layer, were fabricated and measured at room temperature in order to investigate the effects of the PVA (Bi₂O₃-doped) interfacial layer on the main electrical parameters such as the ideality factor (n), zero-bias barrier height (Φ_B0), series resistance (R_s) and interface-state density (N_ss). Electrical parameters of these two diodes were calculated from the current-voltage (I-V) characteristics and compared with each other. The values of Φ_B0, n and R_s for SBDs without polymeric interfacial layer are 0.71 eV, 1.44 and 4775 Ω, respectively. The values of Φ_B0, n and R_s for SBDs with PVA (Bi₂O₃-doped) polymeric interfacial layer are 0.74 eV, 3.49 and 10,030 Ω, respectively. For two SBDs, the energy density distribution profiles of interface states (N_ss) were obtained from forward-bias I-V measurements by taking the bias dependence of R_s of these devices into account. The values of N_ss obtained for the SBD with PVA (Bi₂O₃-doped) polymeric interfacial layer are smaller than those of the SBD without polymeric interfacial layer.     

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.     

The role of 60Co γ-ray irradiation on the interface states and series resistance in MIS structures

The effect of γ-ray exposure on the metal–insulator–semiconductor (MIS) structures has been investigated using the electrical characteristics at room temperature. The MIS structures are irradiated with ⁶⁰Co γ-ray source. The energy distribution of interface states was determined from the forward bias I–V characteristics by taking into account the bias dependence of the effective barrier height and ideality factor. The value of series resistance decreases with increasing dose. Experimental results confirmed that γ-ray irradiation have a significant effect on electrical characteristics of MIS structures.     

Synthesis,characterization, and electrochemical,electrical and gas sensing properties of a novel tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine

A novel tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine (Lu₂Pc₄) (5) has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine (4) with two equiv. of dilithium octakis hexylthiophthalocyanine in amyl alcohol. The phthalonitrile derivative 1 was obtained through the displacement reaction of 4-nitrophthalonitrile with 1,3-dimethoxy-4-tert-butylcalix[4]arene and was converted to the isoindoline derivative 2 by bubbling ammonia gas in dry MeOH. Compound 4 was prepared from 2, 4,5-bis(hexylthio)-1,2-diiminoisoindoline (3), and lutetium acetate in dry DMF. The new compounds and phthalocyanines were characterized by elemental analysis, IR, UV–Vis, ¹H NMR, ESR and MALDI-TOF MS spectra. The electrochemical properties of 4 and 5 have been examined by cyclic voltammetry, and compared. Distinctive differences between the voltammetric behaviour of 4 and 5 were detected. These differences were compatible with the structures of the compounds. A detailed study of the effect of temperature on the d.c. conductivity and impedance spectra (40–10⁵ Hz) of spin coated films of 4 and 5 at temperatures between 290 K and 420 K was carried out. By analyzing the d.c. electrical behaviour of the 5 film, it was found that the experimental data are described by a thermally activated conductivity dependence on temperature with an activation energy of 0.77 eV. The a.c. results give a power law behaviour, σ_a.c. = A(T)ω^s, in which the frequency exponent s decreases with temperature. The sensing behaviour of the film for the online detection of volatile organic solvent vapors was investigated by utilizing an AT-cut quartz crystal resonator. It was observed that the adsorption of the target molecules on the coating surface cause a reversible negative frequency shift of the resonator. Thus, a variety of solvent vapors can be detected by using the 5 film as sensitive coating, with sensitivity in the ppm and response times in the order of several seconds depending on the dipole moment of the organic solvent.     

Controlling the electrical characteristics of Au/n‐Si structure with and without (biphenyl‐CoPc) and (OHSubs‐ZnPc) interfacial layers at room temperature

In order to interpret well whether or not the organic or polymer interfacial layer is effective on performance of the conventional Au/n‐Si (metal semiconductor [MS]) type Schottky barrier diodes (SBDs), in respect to ideality factor (n ), leakage current, rectifying rate (RR ), series and shunt resistances (R_s , R_sh ) and surface states (N_ss ) at room temperature, both Au/biphenyl‐CoPc/n‐Si (MPS₁) and Au/OHSubs‐ZnPc/n‐Si (MPS₂) type SBDs were fabricated. The electrical characteristics of these devices have been investigated and compared by using forward and reverse bias current–voltage (I–V ) characteristics in the voltage range of (?4 V)–(4 V) for with and without (biphenyl‐CoPc) and (OHSubs‐ZnPc) interfacial layers at room temperature. The main electrical parameters of these diodes such as reverse saturation current (I₀ ), ideality factor (n ), zero‐bias barrier height (Φ_B0 ), RR , R_s and R_sh were found as 1.14 × 10^?5 A, 5.8, 0.6 eV, 362, 44 Ω and 15.9 kΩ for reference sample (MS), 7.05 × 10^?10 A, 3.8, 0.84 eV, 2360, 115 Ω and 270 kΩ for MPS1 and 2.16 × 10^?7 A, 4.8, 0.7 eV, 3903, 62 Ω and 242 kΩ for MPS₂, respectively. It is clear that all of these parameters considerably change by using an organic interfacial layer. The energy density distribution profile of N_ss was found for each sample by taking into account the voltage dependence of effective barrier height (Φ_e ) and ideality factor, and they were compared. Experimental results confirmed that the use of biphenyl‐CoPc and OHSubs‐ZnPc interfacial layer has led to an important increase in the performance of the conventional of MS type SBD. Copyright © 2015 John Wiley & Sons, Ltd.     

The origin of negative capacitance in Au/n-GaAs Schottky barrier diodes (SBDs) prepared by photolithography technique in the wide frequency range

Capacitance–voltage (C–V) and conductance–voltage (G/ω–V) measurements of the Au/n-GaAs Schottky barrier diodes (SBDs) in the wide frequency range of 10 kHz–10 MHz at room temperature were carried out in order to evaluate the reason of negative capacitance (NC). Experimental results show that C and G/ω are strong functions of frequency and bias voltage especially in the accumulation region. NC behavior was observed in the C–V plot for each frequency and the magnitude of absolute value of C increases with decreasing frequency in the forward bias region. Contrary to C, G/ω increases with decreasing frequency positively in this region. NC behavior may be explained by considering the loss of interface charges at occupied states below Fermi level due to impact ionization processes. Such behavior of the C and G/ω values can also be attributed to the increase in the polarization especially at low frequencies and the introduction of more carriers in the structure. The values of R_s decrease exponentially with increasing frequency according to literature. In addition, the values of C and G/ω at 1 MHz were corrected to obtain the real diode capacitance by taking the effect of R_s into account.     

Controlling the electrical characteristics of Al/p-Si structures through Bi4Ti3O12 interfacial layer

In this study, the effects of high permittivity interfacial Bi₄Ti₃O₁₂ (BTO) layer deposition on the main electrical parameters; such as barrier height, series resistance, rectifying ratio, interface states and shunt resistance, of Al/p-Si structures are investigated using the current–voltage (I–V) and admittance measurements (capacitance–voltage, C–V and conductance–voltage, G/ω–V) at 1 MHz and room temperature. I–V characteristics revealed that, due to BTO layer deposition, series resistance values that were calculated by both Ohm's law and Cheung's method decreased whereas shunt resistance values increased. Therefore, leakage current value decreased significantly by almost 35 times as a result of high permittivity interfacial BTO layer. Moreover, rectifying ratio was improved through BTO interfacial layer deposition. I–V data indicated that high permittivity interfacial BTO layer also led to an increase in barrier height. Same result was also obtained through C–V data. Obtained results showed that the performance of the device is considerably dependent on high permittivity BTO interfacial layer.     

On the interface states and series resistance profiles of (Ni/Au)–Al0.22Ga0.78N/AlN/GaN heterostructures before and after 60Co (γ-ray) irradiation

The values of interface states (N _SS) and series resistance (R _S) of (Ni/Au)–Al_0.22Ga_0.78N/AlN/GaN heterostructures were obtained from admittance and current–voltage measurements before and after 250 kGy ⁶⁰Co irradiation. The analyses of these data indicate that the values of capacitance and conductance decrease, as the R _S increases with increasing dose rate due to the generation of N _SS. The increase in R _S with increasing dose rate was attributed to two main models. According to the first model, it has been attributed to a direct decrease in the donor concentration in semiconductor material as a result of the elimination of shallow donor states. According to the second model, it is a result of irradiation because of the formation of deep acceptor centers in the semiconductor bulk, and electrons from the shallow donor centers are captured by these acceptors.     

Synthesis, characterization, and electrochemical and electrical properties of novel mono and ball-type metallophthalocyanines with four 9,9-bis(4-hydroxyphenyl)fluorene

The new mono-nuclear 4-5 and ball-type homo-dinuclear 6 phthalocyanines have been synthesized from the corresponding phthalodinitrile derivative 3. The synthesized compounds have been characterized by elemental analysis, UV-vis, IR,(1)H-NMR and MALDI-TOF-mass spectroscopies. The redox behaviours of the complexes were identified by cyclic voltammetry and square wave voltammetry. The temperature dependence of the electronic properties of compounds and adsorption of SO(2) on thin film of 6 were investigated by conductivity measurements using an interdigital transducer structure on glass substrate. Dc conductivity, measured between 300-475 K, is thermally activated with the activation energy ranging between 0.67 and 0.90 eV. The ac conductivity is found to vary with frequency, ω, as ω(s) in which the frequency exponent s decreases with temperature suggesting a hopping conduction mechanism for all compounds. The SO(2) sensing result showed that the spin coated film of 6 exhibits very good SO(2) sensing properties, fast response and recovery rate, high sensitivity and good repeatability.