Effect of seed layer on the growth of rutile TiO2 nanorod arrays and their performance in dye-sensitized solar cells

In order to improve the performance of TiO₂ photoanode-based dye sensitized solar cells (DSSCs), rutile TiO₂ nanorod arrays (NRAs) were grown on SnO₂:F (FTO) conductive glass coated with TiO₂ seed layer by a hydrothermal method. The TiO₂ seed layer was obtained by spin-coating titanium tetraisopropoxide (TTIP) isopropanol solution with concentration in the range of 0~0.075 M. Then the effect of the thin TiO₂ seed layer on the crystal structure and surface morphology of TiO₂ NRAs and the photoelectric conversion properties of the corresponding DSSCs were investigated. It is found that TiO₂ NRAs are vertically oriented, about 1.7 μm long and the average diameter is about 35 nm for the samples derived from TTIP in the range of 0.005~0.05 M, which are more uniform and better separated from each other than those without TiO₂ seed layer (average diameter 35~85 nm). The photoelectric conversion efficiency of DSSCs based on TiO₂ NRAs with TiO₂ seed layer is larger than that without TiO₂ seed layer. Typically, the energy efficiency of DSSCs obtained from the seed solution of 0.025 M TTIP is 1.47%, about 1.8 times greater than that without TiO₂ seed layer. The performance improvement is attributed to the thinner, denser and better oriented NRAs grown on seeded-FTO substrate absorbing more dye and suppressing charge recombination at the FTO substrate/electrolyte interface.     

Preparation of highly photocatalytically active rutile titania nanorods decorated with anatase nanoparticles produced by a titanyl-oxalato complex solution

Rutile phase titania (TiO₂) nanorods and anatase nanoparticles were successfully synthesized from a titanyl-oxalato complex solution prepared using titanium (IV) sulfate and oxalic acid by a hydrothermal process. The impact of various hydrothermal conditions on the formation, morphology, phase, and grain size of the TiO₂ nanocrystals was investigated using fourier transformation infrared spectroscopy, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, and nitrogen adsorption. The photocatalytic activities have been evaluated for the photo-decomposition of phenol under ultraviolet visible illumination. The results revealed that the TiO₂ rutile nanorods decorated with anatase nanoparticles (with ~22% anatase) prepared at 160 °C for 72 h exhibit a higher photocatalytic activity than those pure anatase nanoparticles. This behavior was closely related to the better charge carrier separation in the cases of rutile–anatase mixtures. In addition, the possible growth mechanism and phase development of the rutile nanorods and anatase nanoparticles were illustrated.     

Effect of CdS layers on opto-electrical properties of chemically prepared ZnS/CdS/TiO2 photoanodes

In the present work, CdS nanoparticles as a sensitizer were grown on the spin coated nanoporous TiO₂ film by repeated cycles of a Successive Ionic Layer Adsorption and Reaction (SILAR) method. ZnS layer was coated on the CdS/TiO₂ anodes to act as a protection layer on CdS. The crystallite size of CdS nanocrystals is calculated to be 3 nm from XRD spectra. The optical band gap of the film determined from transmittance spectra decreases from 3.46 to 2.15 eV with the increase in the number of CdS SILAR cycles. SEM and TEM analysis depict the enabled penetration of CdS (1 1 1) nanoparticles into the nanoporous TiO₂ (1 0 1) structure. EDX study confirms the presence of all the elements (Ti, Cd, S, Zn and O) found on the photoanode. The attachment of cubic structured CdS on anatase phase of TiO₂ in the photoanode is verified using Raman spectra. Photoluminescence (PL) study shows that the emission peak corresponding to TiO₂ has been slightly blueshifted due to the interaction of CdS nanoparticles in TiO₂ nanoporous structures. The electrical measurement shows that the dark and light illuminated resistivity of the preferred photoanode is 7.91 and 5.65 Ω cm respectively.     

Enhanced short circuit current density of dye-sensitized solar cells aided by Sr,V co-doped TiO2 particles

This study comes up with a straightforward method for preparing uniform electrodes containing Sr,V co-doped TiO₂ particles for dye-sensitized solar cells (DSCs) applications. The spherical particles with the average diameter around 2.5 µm are assembled from small nanoparticles with the average grain size of 60 nm. X-ray diffraction (XRD) reveals that the introduction of dopants not only inhibits the growth of rutile phase, but also results in smaller primary crystallites, improving the surface area and dye adsorption ability of the electrodes. X-ray photoelectron spectroscopy (XPS) showed that Sr²⁺ and V⁵⁺ ions are well incorporated into the titania crystal lattice without forming specific Strontium and Vanadium compositions. UV–visible spectra show that the co-doped TiO₂ films have lower band gap energy than that of undoped-TiO₂, extending the absorption of TiO₂ into visible region. Isolated energy levels in band structure of TiO₂ as well as local lattice distortions due to dopants introduction are the parameters enhanced the short circuit current density of the cells. The TiO₂ DSC co-doped with 0.075 at% Sr and 1.5 at% V (i.e., S7V15 cell) had the highest circuit current density and power conversion efficiency of 18.57 and 7.76%, respectively, as a result of less recombination, which is demonstrated by electrochemical impedance spectroscopy (EIS).     

A study of ultrasonic spray pyrolysis deposited rutile-TiO2-based metal-semiconductor-metal ultraviolet photodetector

This work uses ultrasonic spray pyrolysis deposition to grow the TiO₂ film on a Si substrate. The TiO₂ film was annealed at 800 °C for 2 h to form rutile phase. X-ray diffraction, Raman spectrum, X-ray photoelectron spectroscopy were used to characterized rutile phase TiO₂. The optical characteristics like refractive index, extinction coefficient and absorption coefficient were measured. The rutile TiO₂-based metal-semiconductor-metal ultraviolet photodetector was fabricated and investigated, including current-voltage characteristic, photoresponsivity, external quantum efficiency, response time, noise equivalent power, and detectivity.     

Influence of Ti film thickness and oxidation temperature on TiO2 thin film formation via thermal oxidation of sputtered Ti film

Single-phase rutile TiO₂ films with good crystallinity were obtained by thermal oxidation of sputtered Ti films on Si and quartz substrates. The influence of the Ti film thickness on oxidation was systematically investigated. A temperature of 823 K was sufficient to fully oxidize Ti films of <0.2 μm in thickness, but 923 K was required for complete oxidation of thicker films. The crystal structure, phase, composition, and optical properties of the TiO₂ films were investigated using X-ray diffraction (XRD), Raman spectroscopy, energy-dispersive X-ray analysis (EDAX), and UV-vis-NIR spectroscopy. XRD and Raman analyses showed that the TiO₂ films are rutile phase. The bandgap of the TiO₂ films decreased with increasing thickness. A growth mechanism for TiO₂ thin films due to thermal oxidation of sputtered Ti films is proposed. Oxidation commences from the surface and proceeds inside the bulk and Ti→TiO₂ phase transformation occurs via different intermediate phases. We found that the oxidation temperature rather than the duration is the dominant factor in the growth of TiO₂ thin films.     

Effect of sol–gel MgO spin-coating on the performance of TiO2-based dye-sensitized solar cells

This paper is concerned with the improvement of dye-sensitized solar cell (DSSC) efficiency upon MgO post-treatment of the TiO₂ electrode. A simple sol–gel technique, involving magnesium acetate as precursor, ethanol as solvent and nitric acid as stabilizer, is applied to prepare a solution of suspended MgO nanoparticles. A single drop of MgO sol at 0.1 M precursor concentration was spin-coated at 3000 rpm for 30 s onto the TiO₂ electrode and sintered at 500 K for 1 h. Dye-loading using N3-dye was applied for 6 h. An increase in the average efficiency of the DSSC from 2.5% to 3.9% (over 50% enhancement) was recorded. Measurements of the dark I–V characteristics, the open circuit voltage decays, the SEM images and the dye absorbance spectra, for both uncoated and MgO-coated electrodes were examined. The improvement of the DSSC efficiency was attributed to an upward shift of the TiO₂ flat band energy and a reduction of the rate of back-transport and recombination.     

Low temperature TiO2 rutile phase thin film synthesis by chemical spray pyrolysis (CSP) of titanyl acetylacetonate

Rutile phase TiO₂ thin films have been synthesized using chemical spray pyrolysis of titanyl acetylacetonate TiAcAc in ethanol at 500 °C. The first part of the paper focuses on the thermal decomposition behavior of the precursor by simultaneous thermogravimetry and differential thermal analysis (TG/DTA) coupled with differential scanning calorimetry (DSC). The second part of the paper focuses on the evolution of TiO₂ thin films and their structural transformation with substrate temperature. XRD revealed amorphous TiO₂ thin film at low substrate temperatures (<350 °C) and on high substrate temperatures anatase (3.84 g/cm³) or rutile (4.25 g/cm³) crystalline structure was obtained. The lattice constant, grain size, microstrain and the dislocation density of the film were obtained from the peak width. FTIR spectra of both anatase and rutile TiO₂ revealed stretching vibration of the Ti–O bond for tetrahedral and octahedral surroundings of the titanium atom. Scanning electron micrograph showed the compactness of the rutile film.     

Effective protection of sequential solution-processed polymer/fullerene bilayer solar cell against charge recombination and degradation

Both charge recombination and degradation in sequential solution processed polymer/fullerene bilayer organic photovoltaics (OPV) are effectively reduced by the insertion of a TiO₂ inter-layer between the bilayer and Al electrode. The polymer/fullerene bilayer composed of a poly(3-hexylthiophene) (P3HT) bottom-layer and a [6,6] phenyl C61-butyric acid methyl ester (PCBM) top-layer shows significant change in morphology due to the substantial inter-penetration of P3HT and PCBM during the thermal annealing process. Consequently, the bilayer surface becomes P3HT rich resulting in significant charge recombination at the bilayer/Al interface of the bilayer OPV. The charge recombination rate of the bilayer OPV is reduced by one order of magnitude upon the insertion of a TiO₂ nanoparticle inter-layer between the bilayer and the Al electrode after the thermal annealing process. In contrast, when the thermal annealing process is conducted after insertion of the inter-layer, the effect of the TiO₂ inter-layer becomes insignificant. The V_OC and efficiency of the bilayer OPV is greatly enhanced from 0.37 to 0.66 V and 1.2% to 3.7%, respectively by utilizing the properly constructed TiO₂ inter-layer in the bilayer OPV. Additionally, insertion of the TiO₂ inter-layer significantly improves the stability of the bilayer OPV. The bilayer OPV with a TiO₂ inter-layer maintains 51% of its initial PCE after storage under dark ambient conditions for 700 h without encapsulation, whereas the bilayer OPV without a TiO₂ inter-layer did not show any solar cell performance after 200 h under the same conditions.     

Transient photovoltage and dark current analysis on enhanced open-circuit voltage of polymer solar cells with hole blocking TiO2 nanoparticle interfacial layer

The open-circuit voltage of bulk heterojunction polymer solar cells utilizing 1,8-diiodooctane (DIO) as a processing additive was greatly improved by using an organic layer coated TiO₂ nanoparticle interfacial layer inserted between the active layer and the Al electrode. The transient photovoltage measurement revealed that there was significant non-geminate recombination at the DIO-processed active layer/Al electrode interface. Reduced open-circuit voltage (V_OC) of the photovoltaic devices and high water contact angle of the DIO-processed active layer showed that the DIO-processed active layer has an undesirable surface composition for the electron collection. The organic layer coated TiO₂ nanoparticle interfacial layer effectively prevented the non-geminate recombination at the active layer/Al interface. As a result, we were able to significantly improve the V_OC and power conversion efficiency from 0.46 V and 2.13% to 0.62 V and 3.95%, respectively.     

Microemulsion-assisted hydrothermal preparation and infrared radiation property of TiO2 nanomaterials with tunable morphologies and crystal form

TiO₂ nanomaterials with adjustable crystalline phases and morphologies were prepared via a mild condition of microemulsion-assisted hydrothermal method. The effects of various reaction conditions, such as the species of inhibitor acid, the concentrations of acid and the reaction temperatures on the crystal forms and morphologies of the TiO₂ nanoparticles were investigated. The particles were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Fourier transformed infrared spectrometer. Experimental results showed that the inhibitor acid of hydrochloric acid in the high concentration was conducive to the formation of rutile TiO₂. Nitric acid led to the formation of anatase TiO₂. The crystallinity of the TiO₂ was improved and the particle size was increased with the increase of the reaction temperature and the acid concentration. The morphologies of the TiO₂ nanoparticles also depended on the species and the concentration of the acids. TiO₂ nanoparticles with various structures of irregular granular, spherical, cosh and donuts-like were presented. Moreover, the infrared emissivity values of the TiO₂ nanoparticles were measured at wavelength of 8–14 μm. The irregular TiO₂ granular with single crystal phase exhibited the optimal infrared radiation property owing to the enhanced scattering ability and attenuation effect.     

High performance dye-sensitized solar cells (DSSCs) achieved via electrophoretic technique by optimizing of photoelectrode properties

This paper describes a simple method utilizing electrophoretic deposition (EPD) of commercial P25 nanoparticles (NPs) films on fluoride-doped tin oxide (FTO) substrate. In this process, voltage and the number of deposition cycles are well controlled to achieve TiO₂ film thickness of around 1.5–26 μm, without any mechanical compression processing. The experimental results indicate that the TiO₂ film thickness plays an important role as the photoelectrode in DSSCs because it adsorbs a large number of dye molecules which are responsible for electrons supply. Furthermore, it was found that effects of the bulk traps and surface states within the TiO₂ films on the recombination of the photo-injected electrons (electron–hole pairs) strongly depend on the TiO₂ electrode annealing temperature. Finally, a DSSC with a 24 μm thick TiO₂ film and annealed at 500 °C produced the highest conversion efficiency (η=6.56%, I_SC=16.4, V_OC=0.72, FF=0.55) with an incident solar energy of 100 mW/cm².     

Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method

Polyaniline (PANI)/TiO₂ nanocomposite samples with various dopant percentages of TiO₂ were synthesized at room temperature using a chemical oxidative method. The samples were characterized by ultraviolet-visible spectrometer, Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and conductivity measurements. Incorporation of TiO₂ nanoparticles caused a slight red shift at 310 nm in the absorption spectra due to the interactions between the conjugated polymer chains and TiO₂ nanoparticles with π–π^? transition. FTIR confirmed the presence of TiO₂ in the molecular structure. In PANI/TiO₂ composites, two additional bands at 1623 cm^?1 and 1105 cm^?1 assigned to Ti–O and Ti–O^–C stretching modes were present. It can be concluded that Ti organic compounds are formed with an alignment structure of TiO₂ particles. XRD patterns revealed that, as the TiO₂ percentage was increased, the amorphous nature disappeared and the composites became more strongly oriented along the (1 1 0) direction, which showed the tetragonal structure of nanocrystalline TiO₂. SEM studies revealed the formation of uniform granular morphology with average grain size of 200 nm for (50%) PANI/TiO₂ nanocomposite samples.     

Template free titiania photoanodes modified with carbon black or multi-wall carbon nanotubes: Thermal treatment at low and high temperature for the fabrication of quasi-solid state dye sensitized solar cells

A simple procedure was developed to prepare modified titiania (TiO₂) photoanodes for dye sensitized solar cells at low and high temperature in order to improve overall cell efficiency. Modification of TiO₂ films achieved by the incorporation of either carbon black powder (CBP) or multi-wall carbon nanotubes (MWCNTs). A small quantity of titanium alkoxide was added in a dispersion of titiania (TiO₂) powder consisting of nanoparticles at room temperature, which after alkoxide׳s hydrolysis helps to the connection between titiania (TiO₂) particles and to the formation of mechanically stable relatively thick films on conductive glass substrates. The absence of surfactant allowed us to prepare films at relatively low temperature (~100 °C), while the effect of sintering at a higher temperature (500 °C) was also studied. The structural properties of the films were examined with porosimetry method and microscopy analysis. Better electrical results were obtained for the MWCNT (0.1 wt%) modified TiO₂ films, with 3.14% and 4.68% conversion efficiencies under 1 sun illumination after treatment at 100 °C and 500 °C, respectively. The enhancement in photocurrent for MWCNT-TiO₂ films compared to pure TiO₂ films is attributed to the improved interconnectivity between TiO₂ nanoparticles, which further improved the electron transport through the film. For carbon doped CBP-TiO₂ cells, lower efficiencies were observed compared to pure TiO₂.     

Photoelectrocatalytic degradation of p-hydroxybenzoic acid at the surface of a titanium/titanium dioxide nanotube array electrode using electrochemical monitoring

In this study, the titanium/titanium dioxide nanotube array (Ti/TiO₂-NTA) electrode was prepared with anodic oxidation of Ti foil electrode. The morphology of Ti/TiO₂-NTA electrode was evaluated with scanning electron microscopy images. The results showed that the inner diameter of nanotubes is below of 100 nm. The electrochemical behavior of the as-prepared Ti/TiO₂-NTA electrode was studied using the cyclic voltammetry. In addition, a significant photoelectrochemical behavior of the p-hydroxybenzoic acid (p-HBA) was observed on the Ti/TiO₂ electrode using the hydrodynamic photoamperometry experiments. Then, the photoelectrocatalytic (PEC) degradation of the p-HBA was performed by this electrode, and compared with photocatalytic (PC), electrooxidation (EC), and direct photolysis by ultra-violet ray. It was found from mechanistic studies that the rate constant for the PEC process of Ti/TiO₂-NTA electrode was higher than other degradation processes. The p-HBA concentration monitoring was carried out with the differential pulse voltammetry. Finally, the effects of the solution pH, applied potential, and the p-HBA concentration on the degradation efficiencies were studied and the results showed that the optimum pH for the photoelectrocatalytic degradation was equal to 7.00. The optimum potential and the optimum concentration were about 0.5 V (vs. Ag|AgCl|KCl (3M) as reference electrode) and 0.129 mM in the studied ranges, respectively.     

Preparation and photocatalytic activity of Ag/bamboo-type TiO2 nanotube composite electrodes for methylene blue degradation

Photocatalysis phenomena in TiO₂ have been intensively investigated for its potential application in environmental remediation. The present work reports improved photocatalytic degradation of methylene blue dye in aqueous solution by using bamboo-type TiO₂ nanotubes deposited with Ag nanoparticles via electrochemical deposition. The photocatalytic processes are performed on Ag-modified TiO₂ bamboo-type nanotube arrays, Ag-modified smooth-walled nanotube arrays, and bare smooth-walled nanotube arrays. Both Ag-modified bamboo-type and smooth-walled nanotube arrays show improved photocatalytic degradation efficiencies (64.4% and 52.6%) compared to smooth-walled TiO₂ nanotubes of the same length (44.4%), due to the enhanced electron–hole seperation and more surface area provided by bamboo ridges. The photocatalytic activity and kinetic behavior of Ag-modified bamboo-type nanotube arrays are also optmized by tuning pulse deposition time of Ag nanoparticles. Bamboo-type nanotubes deposited with Ag nanoparticles via pulse deposition time of 0.5 s/1.5 s shows the highest methylene blue degradation efficiency of 78.5%, which represents 21.9% and 76.8% enhancement of efficiency compared to those of bare bamboo-type and smooth-walled nanotubes, respectively, indicating that a proper amount of Ag nanoparticles on TiO₂ can maximize the photocatalytic processes. In addition, overly long pulse deposition time will not further increase photocatalytic activity due to agglomeration of Ag paticles. For example, when the pulse deposition time is increased to 2 s/6 s, Ag-modified bamboo-type nanotube array exhibits a lower photocatalytic degradation efficiency of 62.9%.     

Structural phase-dependent resistivity of intrinsic-extrinsic co-doped transparent titanium dioxide films

The authors report a method of enhancing the conductivity of TiO₂ films by controlling their structural phases. Thin films of Nb:TiO₂ (TNO) were prepared on glass and silicon substrates by RF sputtering with varying Nb content at 200 °C. It is shown that fine control over the structural phases of TiO₂ is critical for achieving low resistivity. The resistivity values of the films doped with oxygen vacancies and Nb⁺⁵ decreased from 3.8 × 10⁻¹ to 4.1 × 10⁻³ Ω cm when the weight percent of rutile in anatase-rutile phase mixture decreases from 52.8% to 32%. Furthermore, the lowest resistivity value of 2.37 × 10⁻³ Ω cm was obtained for the doped TiO₂ films having single phase anatase structure. The physical processes responsible for the diverse electrical properties are discussed and are associated with the growth conditions. Our result indicates that highly conductive doped-TiO₂ film can be obtained by controlling the anatase phase formation via the growth temperature. The obtained results can significantly contribute to the development of transparent electrodes by RF sputtering, a suitable technique for coating large area substrates.     

Unipolar nonvolatile memory devices with composites of poly(9-vinylcarbazole) and titanium dioxide nanoparticles

Organic-based devices with an 8 × 8 array structure using titanium dioxide nanoparticles (TiO₂ NPs) embedded in poly(9-vinylcarbazole) (PVK) film exhibited bistable resistance states and a unipolar nonvolatile memory effect. TiO₂ NPs were a key factor for realizing the bistability and the concentration of TiO₂ NPs influenced ON/OFF ratio. From electrical measurements, switching mechanism of PVK:TiO₂ NPs devices was closely associated with filamentary conduction model and it was found that the OFF state was dominated by thermally activated transport while the ON state followed tunneling transport. PVK:TiO₂ NPs memory devices in 8 × 8 array structure showed a uniform cell-to-cell switching, stable switching endurance, and a high retention time longer than 10⁴ s.     

The temperature dependent analysis of Au/TiO2 (rutile)/n-Si (MIS) SBDs using current–voltage–temperature (I–V–T) characteristics

In this study, the main electrical parameters of Au/TiO₂(rutile)/n-Si Schottky barrier diodes (SBDs) were analyzed by using current–voltage–temperature (I–V–T) characteristics in the temperature range 200–380 K. Titanium dioxide (TiO₂) thin film was deposited on a polycrystalline n-type Silicon (Si) substrate using the DC magnetron sputtering system at 200 °C. In order to improve the crystal quality deposited film was annealed at 900 °C in air atmosphere for phase transition from amorphous to rutile phase. The barrier height (Φ_b) and ideality factor (n) were calculated from I–V characteristics. An increase in the value of Φ_b and a decrease in n with increasing temperature were observed. The values of Φ_b and n for Au/TiO₂(rutile)/n-Si SBDs ranged from 0.57 eV and 3.50 (at 200 K) to 0.82 eV and 1.90 (at 380 K), respectively. In addition, series resistance (R_s) and Φ_b values of MIS SBDs were determined by using Cheung's and Norde's functions. Cheung's plots are obtained from the donward concave curvature region in the forward bias semi-logarithmic I–V curves originated from series resistance. Norde's function is easily used to obtain series resistance as a function of temperature due to current counduction mechanism which is dominated by thermionic emission (TE). The obtained results have been compared with each other and experimental results show that R_s values exhibit an unusual behavior that it increases with increasing temperature.     

Influence of compact TiO2 layer on the photovoltaic characteristics of the organometal halide perovskite-based solar cells

A series of perovskite-based solar cells were fabricated wherein a compact layer (CL) of TiO₂ of varying thickness (0–390 nm) was introduced by spray pyrolysis deposition between fluorine-doped tin oxide (FTO) electrode and TiO₂ nanoparticle layer in perovskite-based solar cells. Investigations of the CL thickness-dependent current density–voltage (J–V) characteristics, dark current, and open circuit voltage (V_oc) decays showed a similar trend for thickness dependence. A CL thickness of 90 nm afforded the perovskite-based solar cell with the maximum power conversion efficiency (η, 3.17%). Furthermore, two additional devices, perovskite-based solar cell omitting hole transporting materials layer and cell without the TiO₂ nanoparticles, were designed and fabricated to study the influence of the CL thickness on different electron transport paths in perovskite-based solar cells. Solar cells devoid of TiO₂ nanoparticles, but with perovskite and organic hole-transport materials (HTMs), exhibited sustained improvement in photovoltaic performances with increase in the thickness of CL, which is in contrast to the behavior of classical perovskite-based solar cell and common solid state solar cell which showed optimal photovoltaic performances when the thickness of CL is 90 nm. These observations suggested that TiO₂ nanoparticles play a significant role in electron transport in perovskite-based solar cells.