Study on structural phase transitions and relaxation processes of Cs2Co(SO4)2·6H2O and Cs2Zn(SO4)2·6H2O crystals

The structural phase transitions and relaxation processes of Cs₂Co(SO₄)₂·6H₂O and Cs₂Zn(SO₄)₂·6H₂O single crystals were investigated, with the phase transitions of both crystals being determined from NMR data. The spin–lattice relaxation time, T₁, of the ¹³³Cs nucleus in two crystals undergoes a significant change near the phase transition temperature, T_C, and these changes coincide with the changes in the splitting of the ¹³³Cs resonance lines. The variations in the temperature dependence for the splitting of the ¹³³Cs resonance lines and T₁ near T_C are related to changes in the symmetry of surrounding Cs⁺. In addition, the ¹³³Cs T₁ of Cs₂Co(SO₄)₂·6H₂O, which contains paramagnetic ions, was found to be shorter than that of Cs₂Zn(SO₄)₂·6H₂O. This relaxation time is inversely proportional to the square of the magnetic moment of the paramagnetic ions. The differences between the ¹³³Cs T₁ of these compounds are probably due to the differences between the electronic structures of their metal ions.     

Impedance spectroscopy measurements of charge carrier mobility in 4,4'-N,N'-dicarbazole-biphenyl thin films doped with tris(2-phenylpyridine) iridium

The charge carrier mobility of green phosphorescent emissive layers, tris(2-phenylpyridine) iridium [Ir(ppy)₃]-doped 4,4'-N,N'-dicarbazole-biphenyl (CBP) thin films, has been determined using impedance spectroscopy (IS) measurements. The theoretical basis of mobility measurement by IS rests on a theory for single-injection space-charge limited current. The hole mobilities of the Ir(ppy)₃-doped CBP thin films were measured to be 10^− 10–10^− 8 cm²V^− 1 s^− 1 in the 2–7 wt.% Ir(ppy)₃-doped CBP from the frequency dependence of both conductance and capacitance. These hole mobility values are much lower than those of the undoped CBP thin films (~ 10^− 3 cm²V^− 1 s^− 1) because the Ir(ppy)₃ molecules act as trapping centers in the CBP host matrix. These mobility measurements in the Ir(ppy)₃-doped CBP thin films provide insight into the hole injection process.     

Surface tuning for promoted charge transfer in hematite nanorod arrays as water-splitting photoanodes

Hematite (α-Fe₂O₃) nanorod films with their surface tuned by W⁶⁺ doping have been investigated as oxygen-evolving photoanodes in photoelectrochemical cells. X-ray diffraction, field emission scanning electron microscopy, UV-visible absorption spectroscopy, and photoelectrochemical (PEC) measurements have been performed on the undoped and W⁶⁺-doped α-Fe₂O₃ nanorod films. W⁶⁺ doping is found to primarily affect the photoluminescence properties of α-Fe₂O₃ nanorod films. Comparisons are drawn between undoped and W⁶⁺-doped α-Fe₂O₃ nanorod films, WO₃ films, and α-Fe₂O₃-modified WO₃ composite electrodes. A close correlation between dopant concentration, photoluminescence intensity, and anodic photocurrent was observed. It is suggested that W⁶⁺ surface doping promotes charge transfer in α-Fe₂O₃ nanorods, giving rise to the enhanced PEC performance. These results suggest surface tuning via ion doping should represent a viable strategy to further improve the efficiency of α-Fe₂O₃ photoanodes.      

Enhanced photocurrent of nitrogen-doped TiO2 film for dye-sensitized solar cells

Nitrogen (n)-doped titanium dioxide (TiO₂) was prepared with varying doping extent by a general sol–gel process with a pure TiO₂ film as the control sample. The n-doped-2 electrode showed the maximum conversion efficiency with an open-circuit voltage (V_oc) of 0.726 V, a photocurrent (J_sc) of 10.52 mA cm^?2, a fill factor of 63.6%, and an efficiency of 4.86%, compared to 0.751 V, 7.4 mA cm^?2, 67.1%, and 3.73%, respectively, for the undoped (u-doped) TiO₂ electrode. The approximate 23% enhancement in the conversion efficiency of the n-doped-2 TiO₂ electrode-based dye-sensitized solar cells (DSSCs) was mostly ascribed to the increase of light absorption in the near-vis absorbance and partially to the morphological characteristics of the n-doped TiO₂ film. Additionally, the doping type of nitrogen in the TiO₂ lattice was closely studied using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The relation between the doping type and the electron behavior in the DSSCs was also examined.     

Growth of Yb-doped YLiF4 laser crystal by the Czochralski method. Attempt of Yb energy level assignment and estimation of the laser potentiality

YLiF₄ (YLF) single crystals undoped and Yb³⁺-doped with different concentrations were grown by the Czochralski technique under CF₄ atmosphere. Detailed analysis of Yb³⁺-doped YLF spectroscopy were made to contribute to the determination of energy levels in this host. We are dealing with temperature and concentration dependences of both π and σ polarizations of the infrared (IR) absorption and emission spectra. Raman spectra were also used to give an attempt of interpretation of electronic and vibronic levels. The radiative energy transfer (self-trapping) and strong phonon–electron coupling make the assignment of Yb³⁺ energy levels difficult. Evaluation of the laser potentiality of this fluoride host is also presented.     

FeCl3-doped polyvinylidene fluoride

Infrared (350–4000 cm^–1) and optical (1.15×10⁴–2.95×10⁴cm^–1) spectra, differential thermal analysis (DTA) and d.c. electrical resistivity of FeCl₃- doped polyvinylidene fluoride (PVDF) films, over the doping mass fraction range 0 w 0.40, have been measured. The i.r. spectra provided evidence of: (a) the presence of both and phases in the undoped, and a phase in the doped PVDF films; (b) a head-to-head content of 20%; and (c) a different doping mode beyond a 0.25 doping level. The optical spectra resulted in two induced energy bands, and a probable interband electronic transition, due to doping. Dipole relaxation and premelting endothermic peaks were identified by DTA. Electrical conduction is thought to proceed by interpolaron hopping among the polaron and bipolaron states induced by doping. The hopping distance, R _o, is calculated according to the Kuivalainen model. A numerical equation is adopted to formulate the dependence of R _oon doping level and temperature. It is found that R _o< CC separation length. This implies that, in doped PVDF, charge carrier hopping is not an intrachain process.     

Photo-fixation of SO2 in nanocrystalline TiO2 films prepared by reactive DC magnetron sputtering

We report on photo-fixation of SO₂ onto nanostructured TiO₂ thin films prepared by reactive DC magnetron sputtering. The films were exposed to 50 ppm SO₂ gas mixed in synthetic air and illuminated with UV light at 298 and 473 K. The evolution of the adsorbed SO_x species was monitored by in situ Fourier transform infrared specular reflection spectroscopy. Significant photo-fixation occurred only in the presence of UV illumination. The SO₂ uptake was dramatically enhanced at elevated temperatures and then produced strongly bonded surface-coordinated SO_x complexes. The total SO_x uptake is consistent with Langmuir adsorption kinetics. The sulfur doping at saturation was estimated from X-ray photoelectron spectroscopy to be ~ 2.2 at.% at 473 K. These films were pale yellowish and had an optical absorption coefficient being ~ 3 times higher than in undoped film. The S-doped films exhibit interesting oleophobic properties, exemplified by the poor adherence of stearic acid. Our results suggest a new method for sulfur doping of TiO₂ to achieve combined anti-grease and photocatalytic properties.     

Some physical properties of fluorine-doped SnO2 films prepared by spray pyrolysis

Thin films of undoped and fluorine-doped tin oxide have been prepared on fused silica substrates by a spray pyrolysis technique. Structural, optical and electrical properties were studied. Fluorine doping increased the degree of crystallinity and preferred orientation as well as the figure of merit (23.9×10^–3 at 0.5 µm). The refractive index,n, showed a considerable decrease (2.2–1.85) on fluorine doping. The direct allowed transition for fluorine-doped tin oxide was 0.1 eV higher than that of undoped material.     

Nitrogen doped p-type SnO thin films deposited via sputtering

p-Type SnO thin films were fabricated via reactive RF magnetron sputtering on borosilicate substrates with an Sn target and Ar/O₂/N₂ gas mixture. The undoped SnO thin film consisted of a polycrystalline SnO phase with a preferred (1 0 1) orientation; however, with nitrogen doping, the preferred orientation was suppressed and the grain size decreased. The electrical conductivity of the undoped SnO thin films demonstrated a relatively low p-type conductivity of 0.05 Ω⁻¹ cm⁻¹ and it was lowered slightly with nitrogen doping to 0.039 Ω⁻¹ cm⁻¹. The results of the X-ray photoelectron spectroscopy suggested that the nitrogen doping created donor defects in the SnO thin films causing lower electrical conductivity. Lastly, both the undoped and doped SnO thin films had poor optical transmittance in the visible range.     

Effects of samarium dopant on photocatalytic activity of TiO<Subscript>2</Subscript> nanocrystallite for methylene blue degradation

Sm³⁺-doped TiO₂ nanocrystalline was synthesized by a sol–gel auto-combustion method and characterized by X-ray diffraction, Brunauer-Emmett-Teller method (BET), UV–vis diffuse reflectance spectroscopy (DRS), and also photoluminescence (PL) emission spectroscopy. The photocatalytic activity of Sm³⁺–TiO₂ catalyst was evaluated by measuring degradation rates of methylene blue (MB) under either UV or visible light. The results showed that doping with the samarium ions significantly enhanced the photocatalytic activity for MB degradation under UV or visible light irradiation. This was ascribed to the fact that a small amount of samarium dopant simultaneously increased MB adsorption capacity and separation efficiency of electron-hole pairs. The results of DRS showed that Sm³⁺-doped TiO₂ had significant absorption between 400 nm and 500 nm, which increased with the increase of samarium ion content. The adsorption experimental demonstrated that Sm³⁺–TiO₂ had a higher MB adsorption capacity than undoped TiO₂ and adsorption capacity of MB increased with the increase of samarium ion content. It is found that the stronger the PL intensity, the higher the photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions, so that the recombination of photoinduced electrons and holes could be effectively inhibited.     

Structural and electrical properties of soluble conducting poly(3-pentylthiophene)

A solution of processible poly (3-pentylthiophene) (P3PT) was synthesized by chemical polymerization. The structure of the resulting polymer was investigated by gel permeation chromatography (GPC); infrared;¹H and¹³C nuclear magnetic resonance; Ultraviolet visible spectroscopy (UV-Vis) and wide-angle X-ray scattering (WAXS) techniques. It was found that the microstructure of the chains has a low number of irregular couplings and thus has desirable electrical properties. In the small-angle region of X-ray scattering, a pronounced peak was observed with ad (coherence length) value of 1.51 nm for P3PT and 1.835 nm for poly (3-heptylthiophene (P3Hept). Electron spin resonance measurements showed that P3PT has 10¹⁸ spins g^–1, ag value 2.0039, and a H _pp of about 6 Gauss. The Pauli-like susceptibility after doping P3PT with I₂ is of the same order as for poly paraphenylene (PPP) doped with AsF₅, and corresponds to a density of states at the Fermi level about 0.01 states eV^–1 per carbon atom in the thiophene ring. The current-voltage (I–V) characteristics obtained for different temperatures were always linear. The dark room temperature conductivity was 10^–8 Sm^–1 and distinctly increased after doping. The P3PT studied is a good candidate for potential commercial applications.     

A novel route for the synthesis of processable conducting poly(m-aminophenol)

Polymerization of m-aminophenol (mAP) in aqueous NaOH solution was done chemically by using ammonium persulfate (APS) as an oxidative initiator. The product poly(m-aminophenol) (PmAP) was found to be highly soluble in aqueous sodium hydroxide, dimethyl sulfoxide (DMSO) and N,N-dimethyl formamide (DMF). From the intrinsic viscosity measurement, the optimum condition for the polymerization was established with 0.6 M NaOH medium with the ratio of monomer to oxidant as 1:1.5 (mol:mol). The polymer was characterized by FTIR and ¹H NMR spectroscopy, elemental (CHNS) and thermogravimetric (TGA) analyses. From the spectroscopic analysis the structure of the polymer was found to resemble that of hydroxy polyaniline as the polymer contains free –OH groups attached to o/m position in the phenyl ring. The elemental analysis of the polymer also confirmed the same. From TGA study, the polymer was found to be thermally stable. A freestanding film of poly(m-aminophenol) was cast in DMSO solution followed by solvent removal and drying of the film at 100 °C for 7–8 h in an oven. A dc conductivity of 4.8 × 10⁻⁴ S cm⁻¹ was obtained for the synthesized polymer film after doping with H₂SO₄ solution.     

Raman spectroscopic investigations on the kinetics of gelation and densification of Cd- and Pb-doped silica glasses under basic conditions

In the present work, the evolution of the gelation of undoped and Cd²⁺-and Pb²⁺-doped silica sols has been studied. Tetramethyl orthosilicate and cadmium and lead nitrates were selected as suitable precursors for the synthesis of nanoporous undoped and doped silica systems. Raman spectroscopy was used both to follow the different species formed and the structural changes occurring at various stages of the sol-gel transformation. The combination of information obtained from Raman spectra and from textural measurements using nitrogen adsorption-desorption served to investigate the effects of doping metal ion on the structure of both the gels and on the resulting nanoporous silica glasses. Results showed that doping silica materials with different concentrations of Cd²⁺ or Pb²⁺ makes it possible both to decrease the densification time and to control the porosity of the resulting gels and glasses.     

Sintering and properties of SrBi2(Ta1−x V x )2O9 ceramics

The effects of vanadium doping on the sintering, microstructure, dielectric properties, and ferroelectric properties of SrBi₂(Ta_1–x V _x )₂O₉ ceramics were investigated. The densification and grain-growth processes of the vanadium doped ceramics were shifted to a lower temperature range. For the ceramics with relative density 90%, the dielectric constant is 120–125 and 100–130 for the undoped and doped ceramics, respectively, and the dielectric loss tangent is below 1%. As compared with the undoped ceramics, the ferroelectric properties can be significantly improved by doping with an appropriate amount of vanadium and sintering at 1000°C. The variations of dielectric and ferroelectric properties are influenced by the incorporation of vanadium into crystal lattice and several microstructural factors.     

Optical and electrical properties of soluble copolymers of pyrrole-thiophene-3-decylthiophene

Three novel soluble copolymers of pyrrole(P)-thiophene(T)-3-decylthiophene (D) at different molar ratio of comonomers 4 : 1 : 5, 1 : 4 : 5 and 1 : 1 : 2 have been synthesized. NMR, FTIR, UV, emission spectroscopy, GPC, DSC, TGA and conductivity measurements were used to characterize these copolymers. The dark electrical conductivity increases from 3–7 × 10^–6 S/m for undoped samples to 10^–1–10^–2 S/m for samples doped with 4% of iodine, and to 10–10² S/m for 16% of iodine in a form of I₃ ^–.     

Phase transition of Er3+-doped Al2O3 powders prepared by the non-aqueous sol–gel method

The Er³⁺-doped Al₂O₃ powders have been prepared by the non-aqueous sol–gel method using the aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium nitrate, as dopant under isopropanol environment. The phase structure and phase transition of the Er³⁺-doped Al₂O₃ powders were investigated by using thermogravimetry/differential thermal analysis (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The phase contents diagram for the Er-doped Al–O system with the doping concentration up to 5 mol% was described at the sintering temperature from 550 to 1250 °C. There were the three crystalline types of Er³⁺-doped Al₂O₃ phases, γ-, θ- and α-(Al, Er)₂O₃, and the two relative stoichiometric compounds composed of Al, Er, and O, ErAlO₃ and Al₁₀Er₆O₂₄ phases in the Er–Al–O phase contents diagram. The Er³⁺ doping suppressed crystallization of the γ and θ phases and delayed phase transition of the γ → θ and θ → α. The increased Er³⁺ doping concentration and the elevated sintering temperature enhanced the precipitation of the ErAlO₃ and Al₁₀Er₆O₂₄ phases. The preparation procedure for the Er³⁺-doped Al₂O₃ powders in the non-aqueous sol–gel process, including chelating, hydrolysis, peptization, doping and gelation, has a significant effect on the phase formation and its transition for the Er³⁺-doped Al₂O₃ powders.     

X-Ray luminescence of polycrystalline TbO<Subscript>2</Subscript>-doped Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>

This paper examines the effect of doping level on the X-ray luminescence of TbO₂-doped polycrystalline lithium tetraborate. It is shown that, when interpreting such spectra, it is convenient to proceed from the terms of free activator and constituent ions. We demonstrate that the emission lines of Tb³⁺ in doped polycrystalline lithium tetraborate are effectively excited in the band between 350 and 650 nm, which is predominantly due to electron transitions from the ⁵ D ₃ and ⁵ D ₄ excited states to spin-orbital levels of the ⁷ F _J ground multiplet. The emission lines of lithium and boron in single-crystal and polycrystalline undoped lithium tetraborate are effectively excited in the band between 274 and 550 nm.     

Effect of thermal treatment on various characteristics of undoped and V2O5-doped Co3O4/TiO2 catalysts

The thermal treatment of undoped and V₂O₅-doped Co₃O₄/TiO₂ catalysts was studied in the temperature range, 330–600° C both in vacuum and in air. The wide difference in the catalytic behaviour of the two catalysts could be attributed to surface as well as bulk diffusion of the active cobalt oxide particles. Although in both cases the total Co³⁺ ions of various energy states were considered to be the active species for the given reaction, the distribution of various cobalt species, namely Co-t and Co-o, occupying tetrahedral and octahedral sites in the support-defective structure, seemed to be seriously affected by doping with V₂O₅. This dopant was supposed to have two-fold effect: part is incorporated into the surface Co₃O₄ crystallites leading to smaller more mobile particles, easily reducible and more dispersed, and another part diffuses a few atomic layers deeper in the support causing the redistribution of cobalt species. Upon heating, the increased mobility and the increased availability of the support tetrahedral sites may be responsible for the deactivation behaviour. The bulk diffusion enhanced by doping might cause some modification in the porosity characteristics of the titania support.     

Admixture of an s-Wave Component to the d-Wave Gap Symmetry in High-Temperature Superconductors

Neutron crystal-field spectroscopy experiments in the Y- and La-type high-temperature superconductors HoBa₂Cu₃O_6.56, HoBa₂Cu₄O₈, and La_1.81Sr_0.15Ho_0.04- CuO₄ are reviewed. By this bulk-sensitive technique, information on the gap function is obtained from the relaxation behavior of crystal-field transitions associated with the Ho³⁺ ions which sit as local probes close to the superconducting copper-oxide planes. The relaxation data exhibit a peculiar change from a convex to a concave shape between the superconducting transition temperature T _c and the pseudogap temperature T ^* which can only be modeled satisfactorily if the gap function of predominantly d-wave symmetry includes an s-wave component of the order of 20–25%, independent of the doping level. Moreover, our results are compatible with an unusual temperature dependence of the gap function in the pseudogap region (T _c≤T≤T ^*), i.e., a break up of the Fermi surface into disconnected arcs.     

Gamma rays interactions with WO3-doped lead borate glasses

Optical and FT infrared spectral properties of tungsten ions in a host lead borate glass with composition PbO 55%, B₂O₃ 45% (wt%) were studied. The same spectral properties were re-measured after subjecting the samples to successive gamma irradiation. The work was undertaken to justify the state of tungsten ions in such glass system by combined spectral investigations. Optical and FTIR spectral studies were confirmed by investigating electron spin resonance (ESR) of the undoped and WO₃-doped samples before and after gamma irradiation. The optical spectrum of the undoped glass exhibits strong and wide UV absorption bands, which are related to the combined UV spectra of trace iron impurities (Fe³⁺ ions) and that from divalent lead (Pb²⁺) ions. Optical studies of WO₃-doped sample indicate the presence of tungsten ions mostly in the hexavalent W⁶⁺ state. The presence of tungsten ions as structural groups was obtained by comparing the FTIR spectra of the undoped and WO₃-doped samples. ESR spectra confirm the optical and FTIR spectral studies. The studied host lead borate glass has been found to show obvious shielding behavior towards successive gamma irradiation as revealed by the constancy of optical absorption spectral curves.