Synthesis of electrochemically and thermally stable amorphous hole-transporting carbazole dendronized fluorene

A novel amorphous hole-transporting carbazole dendrimer, 2,7-bis[3,6-di(carbazol-9-yl)carbazol-9-yl]-9,9-bis-n-hexylfluorene (G2CF), was synthesized by a divergent approach involving bromination and Ullmann coupling reactions. G2CF showed UV–vis absorption bands at 304 and 332 nm in chloroform solution and the photoluminescence spectra showed a maximum peak at 373 nm in a bluish-purple region. Differential scanning calorimetry (DSC) and cyclic voltammetry (CV) analysis revealed G2CF was an electrochemically and thermally stable amorphous material with a high glass transition temperature (T_g) of 237 °C. The organic light-emitting device having the structure of ITO/G2CF/Alq₃/LiF:Al exhibited a bright green emission with a maximum luminescence of 11,000 cd/m² at 16 V and a turn-on voltage of 5.4 V.     

Synthesis and electrochemical properties of porous LiV3O8 as cathode materials for lithium-ion batteries

In this paper, we report on the synthesis of porous LiV₃O₈ by using a tartaric acid-assisted sol-gel process and their enhanced electrochemical properties for reversible lithium storage. The crystal structure, morphology and pore texture of the as-synthesized samples are characterized by means of XRD, SEM, TEM/HRTEM and N₂ adsorption/desorption measurements. The results show that the tartaric acid plays a pore-making function and the calcination temperature is an important influential factor to the pore texture. In particular, the porous LiV₃O₈ calcined at 300 °C (LiV₃O₈-300) exhibits hierarchical porous structure with high surface area of 152.4 m² g⁻¹. The electrochemical performance of the as-prepared porous LiV₃O₈ as cathode materials for lithium ion batteries is investigated by galvanostatic charge-discharge cycling and electrochemical impedance spectroscopy. The porous LiV₃O₈-300 displays a maximum discharge capacity of 320 mAh g⁻¹ and remains 96.3% of its initial discharge capacity after 50 charge/discharge cycles at the current density of 40 mA g⁻¹ due to the enhanced charge transfer kinetics with a low apparent activity energy of 35.2 kJ mol⁻¹, suggesting its promising application as the cathode material of Li-ion batteries.     

High color rendering white organic light-emitting diodes fabricated using a broad-bandwidth red phosphorescent emitter for lighting applications

High color rendering white organic light-emitting devices (WOLEDs) were developed using a broad-bandwidth red phosphorescent iridium complex, bis[2-(1-naphthyl)benzothiazolato-N,C²′]iridium(III) acetylacetonate [Ir(absn)₂(acac)]. The red phosphorescent emitter Ir(absn)₂(acac) was used to fabricate blue–red and blue–green–red WOLEDs by combining blue-emitting bis[2-(4,6-difluorophenyl)pyridinato-N,C²′]iridium(III) picolinate (FIrpic) and green-emitting tris-fac-(2-cyclohexenylpyridine) iridium (III) [Ir(chpy)₃] in multiple-emissive layers. Mixed host emissive layers were employed using a hole-transport-type host 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA) and an electron-transport-type host 2,6-bis[3-(carbazol-9-yl)phenyl]pyridine (DCzPPy) for efficient charge carrier injection. Di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane (TAPC) and 1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene (BmPyPB) were used as the hole and electron transporting layers, respectively. The effects of the emissive layer thickness and the doping ratios of different color dopants on WOLED performances were investigated. The WOLED based on ITO/TAPC/TCTA:FIrpic (10%):Ir(absn)₂(acac) (4%)/TCTA:Ir(chpy)₃ (9%, 6 nm)/DCzPPy:FIrpic (13%):Ir(absn)₂(acac) (4%)/BmPyPB/LiF/Al exhibited an external quantum efficiency of 10.7%, a power efficiency of 23.0 lm/W, a very high color rendering index (CRI) of 88.1, and a correlated color temperature (CCT) of 2629 K at 1000 cd/m².     

Cobalt-nickel-phosphorus supported on Pd-activated TiO2 (Co-Ni-P/Pd-TiO2) as cost-effective and reusable catalyst for hydrogen generation from hydrolysis of alkaline sodium borohydride solution

Catalytically active, low-cost, and reusable transition metal catalysts are desired to develop on-demand hydrogen generation system for practical onboard applications. Electrolessly deposited Pd-activated TiO₂-supported Co-Ni-P ternary alloy catalyst (Co-Ni-P/Pd-TiO₂) is employed as catalyst in the hydrolysis of alkaline sodium borohydride solution. The catalyst is found to be isolable, redispersible, and reusable in the hydrolysis of alkaline NaBH₄. The reported work also includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy (E_a = 57.0 kJ/mol) and effects of the amount of catalyst, amount of substrate, and temperature on the rate for the catalytic hydrolysis of NaBH₄. Maximum H₂ generation rate of ∼460 mL H₂ min⁻¹ (g catalyst)⁻¹ and ∼3780 mL H₂ min⁻¹ (g catalyst)⁻¹ was measured by the hydrolysis of NaBH₄ at 25 °C and 55 °C, respectively.     

Diphenylamino-substituted derivatives of 9-phenylcarbazole as glass-forming hole-transporting materials for solid state dye sensitized solar cells

The synthesis and properties of glass-forming diphenylamino-substituted derivatives of 9-phenylcarbazole with methoxy groups in the different position of diphenylamino moieties are reported. A comparative study on their thermal, optical, photoelectrical and electrochemical properties is presented. The synthesized compounds exhibit high thermal stability with 5% weight loss temperatures ranging from 344 to 475 °C. The derivatives absorb electromagnetic irradiation in the range of 225–425 nm with the band gaps of 2.94–3.08 eV. The ionization energies of the synthesized compounds range from 5.04 to 5.56 eV. The lowest ionization energies and band gaps are observed for compounds containing para methoxy-substituted phenyl rings of diphenylamino moieties and for disubstituted carbazole derivatives. Charge-transporting properties of the selected compounds were tested by time-of-flight technique. Hole drift mobilities in the amorphous layers of the materials reach 10⁻³ cm²/V s at high electric fields. The derivatives were tested as hole transport materials in solid-state dye sensitized solar cells and showed conversion efficiency up to 0.54%.     

Two step novel chemical synthesis of polypyrrole nanoplates for supercapacitor application

Simple and inexpensive two step novel chemical method for the synthesis of polypyrrole (PPy) nanoplates has been reported. These PPy nanoplates are characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polypyrrole nanoplates exhibit amorphous nature as confirmed from XRD study. Based on SEM and TEM analysis, the formation of the spherical bunches of PPy nanoplates with average size of about 20 nm are inferred. The electrochemical performance of PPy electrode was evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge measurement. A high specific capacitance of 533 F g⁻¹ was obtained within the potential range of −0.4 to 0.6 V in 0.5 M H₂SO₄ solution. Moreover, PPy electrode exhibited high discharge/charge efficiency of 93% and the capacitance retention of 83% at a current density of 10 mA cm⁻² indicating good electrochemical reversibility and rate capability.     

Co-sensitization with near-IR absorbing cyanine dye to improve photoelectric conversion of dye-sensitized solar cells

Two carboxylated cyanine dyes, 3-butyl-2-[3-(1-butyl-5-carboxy-1,3-dihydro-3,3-dimethyl-2H-indol-2-ylidene)-1-propen-1-yl]-1,1-dimethyl-7-[1-[2-[6-(4-morpholinyl)-1,3-dioxo-1H-benz[de]isoquinolin-2(3H)-yl]ethyl]-1H-1,2,3-triazol-4-yl]-1H-Benz[e]indolium iodide (A), 2-[5-(1-butyl-5-carboxy-1,3-dihydro-3,3-dimethyl-2H-indol-2-ylidene)-1,3-pentadienyl]-3-ethyl-1,1-dimethyl-1H-Benz[e]indolium iodide (B), have been prepared and their photophysical and electrochemical properties have been investigated. A, B and their mixtures (AB) were used as sensitizers in nanocrystalline TiO₂ solar cells to improve photoelectric conversion efficiency. It was found that the solar cell sensitized with A3B1 (molar ratio: A:B = 3:1) generated a high power conversion efficiency of 3.0% under AM1.5G illumination (100 mW cm⁻²), indicating that co-sensitization is a promising method to improve the photoelectrical properties of dye-sensitized solar cells.     

Synthesis and study of nanocrystalline Ni-Cu-Zn ferrites prepared by oxalate based precursor method

Nanocrystalline ferrites of compositions Ni_0.5+1.5xCu_0.3Zn_0.2Fe_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized by using oxalate based precursor method at very low temperature. The Ni-Cu-Zn ferrite powder particles were obtained at 450 °C and they exhibit a crystallite size of 16-24 nm. The lattice constants were found nearly equal in all these samples due to minute difference in the ionic radius between Ni²⁺ and Fe³⁺ ions. The thermal analysis has showed the ferrite phase formation at very low temperature 377 °C. The two main spectroscopic bands corresponding to lattice vibrations were observed in the wavelength range from 300 to 1000 cm⁻¹. The IR bands at 570 cm⁻¹ (v₁) and 390 cm⁻¹ (v₂) were assigned to tetrahedral (A) and octahedral [B] groups. The spectroscopic bands shift with the increase of doping concentration. The magnetization was found to decrease with increasing doping concentration. The dielectric constant (?′) and dielectric loss tangent (tan δ) decreased with increase of frequency. The dielectric constant and dielectric loss obtained for the nanocrystalline ferrite samples appeared to be lower than that of the ferrites prepared by other synthesis techniques.     

Transparent conducting oxide films of heavily Nb-doped titania by reactive co-sputtering

Niobium-doped titania (TNO) films of various Nb content were deposited on glass and silicon substrates by reactive co-sputtering of Ti and Nb metal targets. Nb content in the TNO films was varied from 0 to ∼13 at.% (atomic percent), corresponding to Ti_1−xNb_xO₂ with x = 0-0.52, by modulating the Nb target power from 0 to 150 W (Watts). The influence of ion bombardment on the TNO films was investigated by applying an RF substrate bias from 0 to 25 W. The as-deposited TNO films were all amorphous and insulating, but after annealing at 600 °C for 1 h in hydrogen, they became crystalline and conductive. The annealed films crystallized into either pure anatase or mixed anatase and rutile structures. The as-deposited and the annealed films were transparent, with an average transmittance above 70%. Anatase TNO film (Ti_1−0.39Nb_0.39O₂) with Nb 9.7 at.% exhibited a dramatically reduced resistivity of 9.2 × 10⁻⁴ Ω cm, a carrier density of 6.6 × 10²¹ cm⁻³ and a carrier mobility around 1.0 cm² V⁻¹ s⁻¹. In contrast, the mixed-phase Ti_1−0.39Nb_0.39O₂ showed a higher resistivity of 1.2 × 10⁻¹ Ω cm. This work demonstrates that the anatase phase, oxygen vacancies, and Nb dopants are all important factors in achieving high conductivities in TNO films.     

Carbazole-containing enamines as charge transport materials for electrophotography

Synthesis and thermal, optical as well as photoelectrical properties of carbazole-based enamines are reported. The synthesized compounds were found to form glasses with the glass transition temperatures up to 104 °C as characterized by differential scanning calorimetry. Electron photoemission spectra of the synthesized enamines have been recorded and the ionization potentials have been established. The lowest value of ionization potential (5.22 eV) and the best charge transport properties were shown by di(2,2-diphenylvinyl)(9-ethyl-3-carbazolyl)amine. Room temperature hole-drift mobilities in its 50% solid solutions in bisphenol Z polycarbonate established by the xerographic time-of-flight technique were found to be 9 × 10⁻⁵ cm² V⁻¹ s⁻¹ at electric field of 10⁶ V cm⁻¹.     

Thermoelectric properties of Sc- and Y-doped Mg2Si prepared by field-activated and pressure-assisted reactive sintering

Sc- and Y-doped-Mg₂Si samples were reactively sintered by the field-activated and pressure-assisted synthesis (FAPAS) method. The incorporation of these rare-earth elements in this silicide resulted in an n-type semiconductor. The addition of Sc and Y had no discernable effect on the lattice constant of Mg₂Si. The average grain size of the Y-doped Mg₂Si was about 2 μm, which was smaller than that of the sintered pure Mg₂Si. The power factor of samples doped with 2500 ppm Sc was consistently higher than that of pure Mg₂Si in the temperature range of 300-550 K. Similarly, the power factor of 2000 ppm Y doped Mg₂Si samples was higher than that of pure Mg₂Si over the temperature range of 300-675 K; the highest value being about 2.2 × 10⁻³ W m⁻¹ k⁻² at 468 K. This value is about two times that of the undoped Mg₂Si at the same temperature. The thermal conductivity of Mg₂Si doped with 2000 ppm Y was 80% of that of pure Mg₂Si. The highest figure of merit (ZT) for the Y doped (2000 ppm) samples was 0.23 at 600 K which was higher by a factor of 1.6 than the corresponding value of pure Mg₂Si at the same temperature. The results demonstrate the benefits of doping of Mg₂Si with Sc and Y in enhancing its thermoelectric properties.     

Investigations on a nitriding process of molybdenum thin films exposed to (Ar-N2-H2) expanding microwave plasma

Nitriding treatments using various (Ar-N₂-H₂) gas mixtures are performed on thin molybdenum films coated on Si (100) substrates, in an expanding microwave plasma reactor.The electron density measured in (Ar-25%N₂-30%H₂) and (Ar-8%N₂-10%H₂) plasma as well as the electron energy distribution function (EEDF) vary with the distance from the centre of the discharge and are large compared to the corresponding parameters found in (Ar-30%N₂-12%H₂) gas mixture and pure N₂ gas. In such ternary gas mixtures, the mean electron energy ranges between 0.5 and 0.7 eV. A nitride compound of tetragonal-like structure is formed in the whole film thickness of molybdenum heated at 873 K and exposed to (Ar-25%N₂-30%H₂) and (Ar-8%N₂-10%H₂) gas mixtures for exposure times of 20 min duration. It consists of small columnar grains ranging in size from 20 to 30 nm in the growth direction. The nitrogen diffusion profiles are fitted to the Fick's second law by introducing a diffusion coefficient ranging between 5 × 10^− 10 and 5 × 10^− 9 cm²s^− 1 within the accuracy of the method. The diffusion coefficient found from previous measured pressure transients is equal to about 10^− 10 cm²s^− 1. The plasma composition as well as the distance from the centre of the discharge seems to play a role on the reduction of oxides, only. An (Ar-25%N₂-30%H₂) nitriding treatment carried out at 8 cm from the centre of the discharge leads to oxide amount twice lower than the one measured after an (Ar-8%N₂-10%H₂) nitriding treatment carried out at 12 cm from the centre of the discharge. Because of the low ion energies, the reduction of oxides is probably mainly confined to hydrogen species.     

A precursor route to synthesize mesoporous γ-MnO2 microcrystals and their applications in lithium battery and water treatment

MnCO₃ microstructures, including 2.3 μm microplates with the thickness of 200 nm and 3.1 μm microspheres stacked with 50 nm-thick sheets, were hydrothermally prepared in the assistance of sodium dodecyl benzene sulphonate (SDBS) and dodecyl sulfonic acid sodium (SDS), respectively. With the as-synthesized MnCO₃ as precursors followed by annealing at 400 °C for 4 h, mesoporous γ-MnO₂ microplates and microspheres with the pore size of 4-50 nm, which basically preserved the initial shapes, were obtained. The Brunauer-Emmett-Teller surface areas of the as-prepared γ-MnO₂ microplates and microspheres were 52.1 m² g⁻¹ and 50.2 m² g⁻¹, respectively. The electrochemical property tests over Li⁺ batteries showed that the initial discharge capacity of γ-MnO₂ microplates and microspheres were 1997 mAh g⁻¹ and 1533 mAh g⁻¹. Noticeably, even after 100 cycles, the discharge capacity of γ-MnO₂ microplates was still as high as 626 mAh g⁻¹, indicating the decent cycle behavior. In addition, mesoporous γ-MnO₂ was also applied as adsorbents in water treatment, and γ-MnO₂ microplates and microspheres could remove about 55% and 80% of Congo red.     

Synthesis and conductivity of heptadecatungstovanadodiphosphoric heteropoly acid with Dawson structure

A new solid high-proton conductor, heptadecatungstovanadodiphosphoric heteropoly acid H₇P₂W₁₇VO₆₂·28H₂O with Dawson structure was synthesized by the stepwise acidification and the stepwise addition of element solutions. The optimal proportion of component compounds in the synthesis reaction was given. The product was characterized by chemical analysis, potentiometric titration, IR, UV, XRD, ³¹P NMR, TG-DTA and electrochemical impedance spectroscopy (EIS). The results indicate that H₇P₂W₁₇VO₆₂·28H₂O possesses the Dawson structure. EIS measurements show a high conductivity (3.10 × 10⁻² S cm⁻¹ at 26 °C and 75% relative humidity), with an activation energy of 32.23 kJ mol⁻¹ for proton conduction. The mechanism of proton conduction for this heteropoly acid is Vehicle mechanism.     

Electrochemical performance of magnetron sputter deposited LiFePO4-Ag composite thin film cathodes

LiFePO₄ thin films have been sputtered from a pure LiFePO₄ target onto Ag/SS, Ag/Si₃N₄/Si and Si₃N₄/Si substrates. All of the deposited films were annealed at 973 K for 1 hr in H₂/Ar (5 %) atmosphere. Substrate induced microstructural and crystallographic evolutions have been observed by a scanning electron microscope and X-ray diffraction. Energy dispersion spectra and X-ray photoelectron spectra revealed that Ag was mixed in the LiFePO₄ films deposited on Ag under layers. Ceramic metal composite thin films were obtained. The film conductivity (1 × 10^− 3 Scm^− 1) is therefore elevated by an order of six, compared with pure LiFePO₄ (10^− 9 Scm^− 1). The electrochemical measurements of the LiFePO₄-Ag films showed a flat plateau at 3.4 V (v.s. Li/Li⁺) and a reversible capacity of 80 mAh/g. Optimization of Ag contents may further improve the discharge capacity.     

A novel method to synthesize anatase TiO2 nanowires as an anode material for lithium-ion batteries

We demonstrate a simple and novel approach for the synthesis of a kind of anatase TiO₂ nanowires. The method is based on a hydrothermal method under normal atmosphere without using the complex Teflon-lined autoclave, high concentrations NaOH solution and long react time. The as-prepared materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The obtained anatase TiO₂ nanowires show excellent performance. There is a potential plateau at 1.77 and 1.88 V in the process of Li insertion and extraction, and the initial Li insertion/extraction capacities are 283 and 236 mAh g⁻¹ at the density of 20 mA g⁻¹, respectively. In the 20th cycle, the reversible capacities still remain about 216 and 159 mAh g⁻¹ at the current densities of 20 and 200 mA g⁻¹, respectively, and the coulombic efficiency is more than 98%, exhibiting excellent electrochemical performance.     

Effect of Cr7C3 on the mechanical, thermal, and electrical properties of Cr2AlC

In this work, phase pure Cr₂AlC and impure Cr₂AlC with Cr₇C₃ have been fabricated to investigate the mechanical, thermal, and electrical properties. The thermal expansion coefficient is determined as 1.25 × 10⁻⁵ K⁻¹ in the temperature range of 25-1200 °C. The thermal conductivity of the Cr₂AlC is 15.73 W/m K when it is measured at 200 °C. With increasing temperature from 25 °C to 900 °C, the electrical conductivity of Cr₂AlC decreases from 1.8 × 10⁶ Ω⁻¹ m⁻¹ to 5.6 × 10⁵ Ω⁻¹ m⁻¹. For the impure phase of Cr₇C₃, it has a strengthening and embrittlement effect on the bulk Cr₂AlC. And the Cr₂AlC with Cr₇C₃ would result in a lower high-temperature thermal expansion coefficient, thermal conductivity, specific heat capacity and electrical conductivity.     

Studies on the power factor of (Ba,Sr)Co2+xRu4−xO11 compounds

We have prepared polycrystalline single-phase ACo_2+xRu_4−xO₁₁ (A = Sr, Ba; 0 ≤ x ≤ 0.5) using the ceramic method and we have studied their structure, electrical resistivity and Seebeck coefficient, in order to estimate their power factor (P.F.). These layered compounds show values of electrical resistivity of the order of 10⁻⁵ Ωm and their Seebeck coefficients are positive and range from 1 μV K⁻¹ (T = 100 K) to 20 μV K⁻¹ (T = 450 K). The maximum power factor at room temperature is displayed by BaCo₂Ru₄O₁₁ (P.F.: 0.20 μW K⁻² cm⁻¹), value that is comparable to that shown by compounds such as SrRuO₃ and Sr₆Co₅O₁₅.     

Capacitive properties of RuO2 and Ru–Co mixed oxide deposited on single-walled carbon nanotubes for high-performance supercapacitors

Composite electrodes for use in redox supercapacitors were prepared by electrochemical deposition of RuO₂ or the co-deposition of Ru–Co mixed oxides on the surface of single-walled carbon nanotubes. Electrodes coated with the Ru–Co mixed oxide [Ru (13.13 wt%) and Co (2.89 wt%)] or RuO₂, exhibited a similar specific capacitance (∼620 F g⁻¹) at low potential scan rates (10 mV s⁻¹). However, at higher scan rates (500 mV s⁻¹) the mixed metal oxide electrode showed superior performance (570 F g⁻¹) when compared to the RuO₂ electrode (475 F g⁻¹). This increase in capacitance at high scan rates is attributed to the role of the Co in providing enhanced electronic conduction.     

Investigation on the synthesis and quantum confinement effects of pure and Mn added Zn(1−x)CdxS nanocrystals

Zn_(1−x)Cd_xS and Zn_(1−x)Cd_xS:Mn²⁺ semiconductor quantum dots (2-4 nm) have been prepared by a novel solvothermal route assisted microwave heating method. The growth parameters governing the smaller size and higher yield have been optimized. The synthesized QDs exhibit a significant blue shift as compared to their corresponding bulk counterpart in the UV-vis optical absorption spectrum. The dielectric constant value varies from 2.79 to 6.17 (at 40 °C, 1 kHz) depending upon the composition of the alloy; lower value corresponds to Zn_0.75Cd_0.25S:Mn²⁺ and the higher value corresponds to Zn_0.25Cd_0.75S:Mn²⁺. The crystallite size to exciton bohr radius ratio being <1 indicates a strong quantum confinement effect in both CdS and ZnS QDs. The quantum confinement effect exists in the sequence of ZnS:Mn²⁺ < Zn_(1−x)Cd_xS:Mn²⁺ (x < 0.5) < ZnS < Zn_(1−x)Cd_xS < CdS < CdS:Mn²⁺.