Charge recombination reduction in dye-sensitized solar cells by depositing ultrapure TiO2 nanoparticles on “inert” BaTiO3 films

Ultrapure TiO₂ nanoparticles (∼5 nm in size) were supported on “inert” BaTiO₃ films by TiCl₄ treatment, which was used to fabricate dye-sensitized solar cells (DSSCs). The optimized electrode, designated as BaTiO₃/TiO₂(4), was obtained upon four cycles of TiCl₄ treatment. DSSC with BaTiO₃/TiO₂(4) electrode exhibits superior power conversion efficiency (PCE) compared to that with conventional anatase TiO₂ (∼25 nm in size) electrode. The interfacial charge recombination kinetics was investigated by electrochemical impedance spectroscopy (EIS) and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). In contrast to DSSC with anatase TiO₂ electrode, the dramatically enhanced electron lifetime for DSSC with BaTiO₃/TiO₂(4) electrode could be attributed to the decrease of recombination reaction at the TiO₂ photoelectrode/electrolyte interface. It is proposed that the lower interfacial charge recombination can be related to the relatively shallower trap distributions in DSSC with BaTiO₃/TiO₂(4) electrode.     

Preparation of high surface area LaTiO2N photocatalyst

Nanocrystalline LaTiO₂N with a surface area of 27.5 m²/g was synthesized by nitridation of amorphous La₂O₃/TiO₂ composite powder at 900 °C for 8 h using NH₃ as the reactant gas. X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the as-prepared LaTiO₂N nanocrystals had a mean diameter of about 30 nm. It was found that the absorption edge of the oxynitride is significantly red-shifted compared with that of La₂Ti₂O₇ as increasing the nitridation temperature. The UV–vis absorption spectra indicated that the synthesized oxynitrides displayed good light absorption properties not only in the ultraviolet light but also in the visible-light region.     

Photoconductive properties of organic-inorganic hybrid perovskite (C6H13NH3)2(CH3NH3)m − 1PbmI3m + 1:TiO2 nanocomposites device structure

Photoconductive devices, with remarkable photoconductive performance, of fluorine doped tin oxide/TiO₂/(C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2):TiO₂/Pt were fabricated. An electron injection mechanism from the (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2) to TiO₂ was proposed for the photoconductive effects, where organic-inorganic hybrid perovskite (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2), self-organized into mesoscopic TiO₂ films from solution directly, served as the electron donor. The photoconductive performance of the devices can be adjusted by the inorganic sheet thickness (tuned by m) of the hybrid perovskite. The photocurrent value increased as m value increased at the same illumination. Further, when bias voltage was 1.0 V, the ratio of photocurrent and dark current for (C₆H₁₃NH₃)₂(CH₃NH₃)_2⁻ Pb₂I₇:TiO₂ reached as high as 7.05 × 10³. The devices could be potentially used as light detectors and light-controlled switch.     

Synthesis and characterization of beta barium borate thin films obtained from the BaO-B2O3-TiO2 ternary system

This work reports on the synthesis and the structural and optical characterization of beta barium borate (β-BBO) thin films containing 4, 8 and 16 mol% of titanium oxide (TiO₂) deposited on fused silica and silicon (0 0 1) substrates using the polymeric precursor method. The thin films were characterized by X-ray diffraction, Raman spectroscopy, atomic force microscopy and scanning electron microscopy techniques. The optical transmission spectra of the thin films were measured over a wavelength range of 800-200 nm. A decrease was observed in the band gap energy as the TiO₂ content was raised to 16 mol%. Only the β-BBO phase with a preferential orientation in the (0 0 l) direction was obtained in the sample containing 4 mol% of TiO₂ and crystallized at 650 °C for 2 h.     

Self-limiting growth of anatase TiO2: A comparison of two deposition techniques

Self-limiting deposition of titanium dioxide thin films was accomplished using pulsed plasma-enhanced chemical vapor deposition (PECVD) and plasma-enhanced atomic layer deposition (PEALD) at low temperatures (T < 200 °C) using TiCl₄ and O₂. TiCl₄ is shown to be inert with molecular oxygen at process conditions, making it a suitable precursor for these processes. The deposition kinetics were examined as a function of TiCl₄ exposure and substrate temperature. The quality of the anatase films produced by the two techniques was nominally identical. The key distinctions are found in precursor utilization and conformality. Pulsed PECVD requires 20 times less TiCl₄, while PEALD must be used to uniformly coat complex topographies.     

Dye-sensitized solar cells with TiO2 nanocrystalline films prepared by conventional and rapid thermal annealing processes

Titanium oxide (TiO₂) thin films are prepared by the sol-gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide -coated glass substrates for application as the work electrode for the dye-sensitized solar cells (DSSC). TiO₂ thin films are crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °Cmin⁻¹ and 600 °Cmin⁻¹, respectively. The TiO₂ thin films are characterized by X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller analysis. Based on the results, the TiO₂ films crystallized by RTA show better crystallization, higher porosity and larger surface area than those of CTA. The short-circuit photocurrent and open-circuit voltage values increased from 5.2 mAcm⁻² and 0.6 V for the DSSC with the CTA-derived TiO₂ films to 8.3 mAcm⁻² and 0.68 V, respectively, for the DSSC containing RTA-derived TiO₂ films.     

Fabrication of low-resistivity and gold-colored TiN films by halide chemical vapor deposition with a low [NH3]/[TiCl4] flow ratio

This work describes the preparation of titanium nitride (TiN) films on Si (111) substrates by atmospheric pressure halide chemical vapor deposition (AP-HCVD). Various TiN films were obtained by exploiting TiCl₄ + NH₃ gas chemistry with flow ratios [NH₃]/[TiCl₄] from 0.2 to 1.4, and deposition temperatures (T_d) from 600 to 900 °C. When T_d = 800 °C gold-colored films with electrical resistivities of under 100 μΩ cm were formed at almost all of the investigated [NH₃]/[TiCl₄] flow ratios. In particular, a lowest resistivity of about 23.7 μΩ cm, which is quite close to that of bulk TiN, was achieved using an [NH₃]/[TiCl₄] flow ratio of 0.3. Atomic force microscopy indicated that the root mean square surface roughness of that film was only about 5.1 nm. Under the same [NH₃]/[TiCl₄] flow ratio as above, X-ray diffraction analyses revealed the presence of a cubic TiN phase with a preferred orientation of (200) for T_d ≤ 800 °C, while additional (111) and (220) orientations emerged when the film was deposited at 900 °C. In conclusion, a low resistivity (< 100 μΩ cm) TiN film can be formed by AP-HCVD with very low [NH₃]/[TiCl₄] flow ratios 0.3-1.4.     

Synthesis of carbon-doped TiO2 nanoparticles using CO2 decomposition by thermal plasma

This study examined the synthesis of carbon-doped titanium dioxide using TiCl₄ and CO₂ as titanium and carbon sources, respectively, by thermal plasma at atmospheric pressure. The effect of the CO₂ gas flow rate on the preparation of TiO₂ was investigated. The results showed that the decomposition rate of CO₂ was 90% at a CO₂ gas flow rate of 1 L/min. When TiCl₄ was added to produce TiO₂, the decomposition rate of CO₂ reached 95% at a CO₂ gas flow rate of 1 L/min. The resulting powders contained mixed anatase and rutile phases with particle sizes ranging from 20 to 50 nm. The carbon in the CO₂ acted as a dopant to produce the carbon-doped TiO₂. The prepared samples were mainly characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area measurements and ultraviolet-visible spectroscopy.     

Perovskite oxynitride LaTiOxNy thin films: Dielectric characterization in low and high frequencies

Lanthanum titanium oxynitride (LaTiO_xN_y) thin films are studied with respect to their dielectric properties in low and high frequencies. Thin films are deposited by radio frequency magnetron sputtering on different substrates. Effects of nitrogen content and crystalline quality on dielectric properties are investigated. In low-frequency range, textured LaTiO_xN_y thin films deposited on conductive single crystal Nb-STO show a dielectric constant ε′ ≈ 140 with low losses tanδ = 0.012 at 100 kHz. For the LaTiO_xN_y polycrystalline films deposited on conductive silicon substrates with platinum (Pt/Ti/SiO₂/Si), the tunability reached up to 57% for a weak electric field of 50 kV/cm. In high-frequency range, epitaxial LaTiO_xN_y films deposited on MgO substrate present a high dielectric constant with low losses (ε′ ≈ 170, tanδ = 0.011, 12 GHz).     

Surface treatment of TiO2 films for dye-sensitized solar cells using atmospheric-pressure non-equilibrium DC pulse discharge plasma jet

In this paper, we report the utilization of the DC pulse discharge plasma jet technique as a means for the preparation of titanium oxide (TiO₂) films on fluorine dope tin oxide (FTO) coated glass substrates used for dye-sensitized solar cells (DSCs). The TiO₂ film made on these experimental bases exhibited the BET specific surface area of 95 m²/g, the pore volume of 0.3 cm²/g and the TEM particle size of ∼25 nm. The DSCs made by the TiO₂ film exhibited an energy conversion efficiency of 5.7% at 100 mW/cm² light intensity. Consequently, we believe that the optimization between the specific surface area and photocurrent density of TiO₂ film was achieved by the plasma surface treatment which also contributed to the improvement of energy conversion efficiency of DSCs.     

Preparation of monoclinic BiVO4 thin film by citrate route for photocatalytic application under visible light

A monoclinic BiVO₄ (mBiVO₄) film composed of nanoparticles with a size of 100 nm was prepared via a citrate-precursor chemical route. The BiVO₄ film was characterized by X-ray diffraction, scanning electron microscopy and absorption spectra. It was found that the mBiVO₄ film showed a photocatalytic activity of Acid Orange 7 (AO7) degradation in aqueous solution under visible-light irradiation (λ > 400 nm). The degradation efficiency was 78.9% in 3 h and basically remained constant in 10 repeated batch runs. The results demonstrated that the mBiVO₄ film had a high photocatalytic activity under visible light and good durability in repeated use.     

Preparation of TiO2 paste using poly(vinylpyrrolidone) for dye sensitized solar cells

The surface morphology of titanium oxide (TiO₂) films as a photoanode in dye sensitized solar cells plays a vital role in converting light to electricity. Therefore, TiO₂ films were prepared using TiO₂ paste with different compositions of poly(vinylpyrrolidone) (PVP) as a binder to optimize their physico-chemical properties. The paste was prepared with commercial TiO₂ powder mixed with acetylacetone, PVP, 4-octylphenol polyethoxylate, acetic acid and ethanol. The chemical composition remains the same for all pastes except PVP. The quantity of the PVP was optimized in such a way that it provides a thick film with a good network connection. The impact of the quantity of PVP in the TiO₂ paste was analyzed. The prepared TiO₂ film structure was characterized by X-ray diffraction. The surface morphology was analyzed by scanning electron microscopy. The electrochemical performance of the prepared TiO₂ as a photoanode was also investigated. Among the four different photoanodes, the cells fabricated with a TiO₂ film prepared with 0.4 g of PVP exhibited the highest power conversion efficiency of 6.77%, short-circuit photocurrent density and open circuit voltage of 12.38 mA/cm² and 0.77 V, respectively.     

Preparation and characterization of spray deposited n-type WO3 thin films for electrochromic devices

The n-type tungsten oxide (WO₃) polycrystalline thin films have been prepared at an optimized substrate temperature of 250 °C by spray pyrolysis technique. Precursor solution of ammonium tungstate ((NH₄)₂WO₄) was sprayed onto the well cleaned, pre-heated fluorine doped tin oxide coated (FTO) and glass substrates with a spray rate of 15 ml/min. The structural, surface morphological and optical properties of the as-deposited WO₃ thin films were studied. Mott-Schottky (M-S) studies of WO₃/FTO electrodes were conducted in Na₂SO₄ solution to identify their nature and extract semiconductor parameters. The electrochromic properties of the as-deposited and lithiated WO₃/FTO thin films were analyzed by employing them as working electrodes in three electrode electrochemical cell using an electrolyte containing LiClO₄ in propylene carbonate (PC) solution.     

Hydrothermal growth of double-layer TiO2 nanostructure film for quantum dot sensitized solar cells

A double-layer (DL) film with a TiO₂ nanosheet-layer on a layer of TiO₂ nanorod-array, was synthesized on a transparent conductive fluorine-doped tin oxide substrate by a two-step hydrothermal method. Starting from the precursors of NaSeSO₃, CdSO₄ and the complex of N(CH₂COOK)₃, CdSe quantum dots (QDs) were grown on the DL-TiO₂ substrate by chemical bath deposition method. The samples were characterized by X-ray diffraction, Scanning electron microscopy, Energy dispersion spectroscopy, and their optical scattering property was measured by light reflection spectrometry. Some CdSe QDs sensitized DL-TiO₂ films serve as the photoanodes, were assembled into solar cell devices and their photovoltaic performance were also characterized. The short circuit current and open-circuit voltage of the solar cells range from 0.75 to 4.05 mA/cm² and 0.20 − 0.42 V under the illumination of one sun (AM1.5, 100 mW/cm²), respectively. The photocurrent density of the DL-TiO₂ film is five times higher than that of a bare TiO₂ nanorod array photoelectrode cell.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Highly Efficient Water Oxidation Photoanode Made of Surface Modified LaTiO2N Particles

An improved variation of highly active/durable O₂‐evolving LaTiO₂N powder‐based photoelectrode has been fabricated by pre‐cleaning the powder with mild polysulfonic acid and by homogeneous deposition of CoO_x co‐catalyst aided by microwave annealing. The treatment in aqueous solution of poly(4‐styrene sulfonic acid) results in removal of surface LaTiO₂N layers, forming fine pores in the crystallites. The CoO_x co‐catalyst by microwave deposition in Co(NH₃)₆Cl₃/ethylene glycol homogeneously covers the particle surface. The LaTiO₂N powder is fabricated into particle‐transferred electrodes on Ti thin film supported on solid substrate. The modified LaTiO₂N grains on the electrode serve as a highly active O₂‐evolving photoanode achieving 8.9 mA cm^?2 of the photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) in 0.1 m NaOH (pH 13) under solar‐simulator irradiation Airmass 1.5 Global (AM 1.5G). The activity has been much improved, compared with conventional LaTiO₂N treated in mineral acid or with CoO_x deposited by impregnation. The new electrode also exhibits better durability in fixed‐potential chronoamperometric tests under AM 1.5G irradiation.     

Photoelectrochemical and optical properties of N-doped TiO2 thin films prepared by oxidation of sputtered TiNx films

Nitrogen-doped titanium dioxide thin films with visible light photoresponse were prepared by oxidation of sputtered TiN_x films, whose nitrogen contents can be easily changed by controlling the volume ratio of N₂/(Ar + N₂) during reactive direct current (DC) magnetron sputtering process. The reference TiO₂ sample was also deposited by the same method under Ar/O₂ gas mixture. The as-prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoemission spectroscopy, UV-vis spectrophotometry and photoelecrochemical measurements. The formation of anatase type TiO₂ is confirmed by XRD. SEM measurement indicates a rough surface morphology with sharp, protruding modules after annealing treatment. Optical properties reveal an extended tailing of the absorption edge toward the visible region due to nitrogen presence. The band gap of the N-doped sample is reduced from 3.36 eV to 3.12 eV compared with the undoped one. All the N-doped samples show red shift in photoresponse towards visible region and improved photocurrent density under visible irradiance is observed for the N-doped samples.     

New lead vanadium phosphate with langbeinite-type structure: Pb1.5V2(PO4)3

The new lead vanadium phosphate Pb_1.5V₂(PO₄)₃ was synthesized by solid state reaction and characterized by X-ray powder diffraction, electron microscopy, and magnetic susceptibility measurements. The crystal structure of Pb_1.5V₂(PO₄)₃ (a = 9.78182(8) Å, S.G. P2₁3, Z = 4) was determined from X-ray powder diffraction data and belongs to the langbeinite-type structures. It is formed by corner-linked V³⁺O₆ octahedra and tetrahedral phosphate groups resulting in a three-dimensional framework. The lead atoms are situated in the structure interstices and only partially occupy their positions. An electron microscopy study confirmed the structure solution. Magnetic susceptibility measurements revealed Curie-Weiss (CW) behavior for Pb_1.5V₂(PO₄)₃ at high temperature whereas at around 14 K an abrupt increase on the susceptibility was observed.     

A new method to prepare high-surface-area N-TiO2/activated carbon

A new method, combining impregnation and vapor-hydrolysis, was developed to prepare hybrid photocatalyst: nitrogen doped TiO₂ coated activated carbon (N-TiO₂/AC). The activated carbon (AC) was impregnated into titanium tetraethoxide/urea/methanol solution, and then the impregnated AC powder was kept in water vapor at 90 °C for 3 h for hydrolysis. Then it was calcinated to fabricate N-TiO₂/AC. Transmission electron microscopy (TEM) results showed that the nitrogen doped TiO₂ (N-TiO₂) in the as-synthesized hybrid was anatase TiO₂ powder with 10-20 nm in grain size, and the bandgap was about 3.08 eV. Moreover, the hybrid photocatalyst (8 wt.% N-TiO₂) had high specific surface area that was up to 1321 m²/g. The hybrid photocatalyst is expected to have high photocatalytic performance with visible irradiation.     

Synthesis of Co3O4 nanoparticles via the CTAB-assisted method

Cobalt oxide (Co₃O₄) nanoparticles were successfully synthesized by the cetyltrimethylammonium bromide (CTAB)-assisted method at normal pressure for the first time. The structure and morphology of the as-prepared Co₃O₄ nanoparticles were characterized by powder X-ray diffracton (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N₂-sorption analysis. XRD studies indicated that the as-prepared product was well-crystallized cubic phase of Co₃O₄ with a cell constant of α = 8.0722 Å. The EM images showed that the obtained Co₃O₄ sample consisted of dispersive quasi-spherical particles with the size ranged from 15 to 25 nm.