Fabrication of TiO2 compact layer precursor at various reaction times for dye sensitized solar cells

A compact layer is used to increase the photoelectric conversion efficiency on DSSCs due to it can improve the transparent conduction oxides (TCOs) surface and prevent the electrolyte from directly contacting the ITO (Indium Tin Oxide) substrate. In this study, DSSCs with compact layer reacting for three hours are compared to those without compact layer, where the short-circuit current and solar energy conversion efficiency are improved by 22%, and 26%, respectively. Based on electrochemical impedance spectra (EIS) measurements, we clarify that the compact layer can decrease the charge interfacial resistance and the leakage current due to the fact that the dense TiO₂ nanoparticles can effectively prevent charge transport from the photoanode to the ITO substrate. We compared different reacting times for the formation of the compact layer, and showed that the quantum efficiency of DSSC is higher when a 3 h reacting time is adopted with respect to a 24 h processing time. A study of the various molar ratios of the precursor solution has been done. The data showed that the 1 M is the optimal molar ratio. We also studies the compact layer formation on FTO with respect to ITO, showing that the FTO substrate has higher photoelectric conversion efficiency.     

Binder-free MWCNT/TiO2 multilayer nanocomposite as an efficient thin interfacial layer for photoanode of dye sensitized solar cell

Multiwalled carbon nanotube/TiO₂ multilayer nanocomposite was successfully deposited on the fluorine-doped tin oxide (FTO) glass via layer-by-layer assembly technique to modify interfacial contact between the FTO surface and nanocrystalline TiO₂ layer as well as carbon nanotube/TiO₂ contacts in photoanode of dye sensitized solar cell. Using this approach, binder-free interfacial thin film was developed with nonagglomerated, well-dispersed MWCNTs on FTO and into TiO₂ matrix and with maximum covering of TiO₂ nanoparticles on MWCNTs. Introduction of MWCNTs/TiO₂ interfacial layer into the TiO₂ photoanode increased short circuit current density (J_sc) from 11.90 to 17.25 mA/cm² and open circuit voltage (V_oc) from 730 mV to 755 mV, whereas there was no notable change in the fill factor (FF). Consequently, power conversion efficiency (η) was enhanced from 5.32% to 7.53%, yielding a 41.5% enhancement. The results suggest that our simple strategy can integrate reduction of back electron reaction at FTO/TiO₂ interface with the effective charge transport ability of carbon nanotubes and possessing high surface area for efficient dye loading.     

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 of ZnO nanostructure films by thermal evaporation approach and their application in dye-sensitized solar cells

Zinc oxide (ZnO) films were prepared successfully by simple thermal evaporation of zinc acetate dihydrate at low temperature onto FTO (fluorine-doped tin oxide) glass substrates coated with thin ZnO seed layer. The synthetic parameter such as temperature was found to determine the morphology of nanostructures. ZnO nanorod (NR) and nanoparticle (NP) films have been synthesized at 245 and 350 °C, respectively, for 6 h. The dye-sensitized solar cells (DSSCs) were fabricated using the ZnO nanostructure films as photosensitized electrodes. A maximum photoelectric conversion efficiency (PCE) of 1.56%, and short-circuit photocurrent density of 5.12 mA/cm² were achieved with the ZnO NP-based DSSC. The PCE increase was ascribed to the reduced recombination loss and prolonged electron lifetime according to electrochemical impedance spectroscopy (EIS).     

The relation between TiO2 nano-pastes rheology and dye sensitized solar cell photoanode efficiency

TiO₂ nanoparticle pastes for screen printed semiconductive photoanodes of dye sensitized solar cells were prepared with different content (from 0 to 9 wt%) of ethyl cellulose and evaluated by rheology measurements. The effect of ethyl cellulose content in the paste is crucial for printed and sintered TiO₂ photoanode properties as thickness, roughness and amount of adsorbed dye, measured by profilometry, atomic force microscopy, IR and UV‐Vis spectroscopy. Moreover, the expressive correlation among paste rheology, layer properties and the final dye sensitized solar cell efficiency depending on the initial ethyl cellulose content was found, including correlations of the properties local maxima positions. The highest efficiency was achieved for the TiO₂ paste with 6.5 wt% of ethyl cellulose, where initial paste viscosity and thixotropy, printed layer thickness, roughness and amount of adsorbed dye achieved the local maxima (~40 Pa.s, 4.5 µm, 24 nm, 1.92×10⁻⁸ mol/cm², respectively) that indicates the optimal structure of the oxide photoanode layer. The results confirm the importance of controlled ethyl cellulose concentration and rheological properties of applied pastes for higher DSSC efficiency achievement.     

Tunable TiO2 films for high-performing transparent Schottky photodetector

We demonstrate the transparent Schottky photodetector of the configuration Cu/TiO₂/FTO unveiling superior photodetection properties. The improved performance of fabricated photodetector was ascribed to high quality rutile-nanocrystalline TiO₂ films with very high absorption coefficient (~6×10⁵ cm⁻¹) and excitonic localized states. The existence of such localized states in TiO₂ Schottky device offered fastest response time of 1.12 ms suggesting their application in fast switching photodetectors. In addition, the photodetectors showed high responsivity of the value 0.897 A/W and detectivity 4.5×10¹² Jones. This transparent TiO₂ design would provide a functional route for various photoelectric device applications.     

Photoelectrochemical characteristics of TiO2 nanorod arrays grown on fluorine doped tin oxide substrates by the facile seeding layer assisted hydrothermal method

TiO2 nanorod arrays (NRAs) were prepared on fluorine doped tin oxide (FTO) substrates by a facile two-step hydrothermal method. The nanorods were selectively grown on the FTO regions which were covered with TiO2 seeding layer. It took 5 h to obtain the compact arrays with the nanorod length of ~2 μm and diameter of ~50 nm. The photoelectrochemical (PEC) properties of TiO2 NRAs are also investigated. It is demonstrated that the TiO2 NRAs indicate the good photoelectric conversion ability with an efficiency of 0.22% at a full-wavelength irradiation. A photocurrent density of 0.21 mA/cm2 is observed at 0.7 V versus the saturated calomel electrode (SCE). More evidences suggest that the charge transferring resistance is lowered at an irradiation, while the flat-band potential (Vfb) is shifted towards the positive side.     

Effects of annealing technique and TiO2 seed layer on the phase composition of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 film

The lead magnesium niobate–lead titanate (PMN–PT) thin films with and without the TiO₂ seed layer were prepared by a pulsed laser deposition (PLD) deposited on Pt/Ti/SiO₂/Si substrates. The films were treated by two-step annealing and normal annealing with rapid thermal annealing (RTA). The effects of two-step annealing and the TiO₂ seed layer on the phase composition of PMN–PT films were studied. The results show that the PMN–PT film with TiO₂ seed layer can gain a pure perovskite phase with a high (1 0 0) preferential orientation after the two-step annealing technique.     

Performance analysis of dye solar cell with additional TiO2 layer under different light Intensities

Deployment of dye solar cells (DSCs) for building integration application would require a highly efficient solar cell that work well in diffused light. In order to improve the efficiency of dye solar cell, an additional layer of ultrathin anatase titanium dioxide (TiO₂) has been deposited for strengthening the adhesion of the porous TiO₂-based photo electrode to the conductive transparent substrate, which can lead to an enhancement in electron transportation. Fabricated cells of 1 cm² area were tested under different light intensities (100, 33 and 10 mW cm⁻²) and characterized by scanning electron microscopy (SEM), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). Analysis showed an increment in overall quantum conversion efficiency (η), as high as 35% compared to the standard cell without the additional layer of TiO₂. EIS analysis has proven that the additional ultrathin anatase layer has improved the collection efficiency (Φ_COLL) as the result of the enhancement in both electron transport and lifetime within the porous TiO₂ film which translated into better conversion efficiency of DSCs.     

Stacked graphene–TiO2 photoanode via electrospray deposition for highly efficient dye-sensitized solar cells

A series of TiO₂–graphene stacked photoanodes for dye-sensitized solar cells (DSSCs) were fabricated by electrospray (E-spray) deposition. Among devices incorporating single graphene layer with different deposition times, device with 1 min graphene deposition gave the best performance. For multi-graphene-layer involved devices, best result was obtained with 3 layers of graphene. The working principles were analyzed by scanning electron microscopy, transmittance spectra, electrochemical impedance spectroscopy and incident-photo-conversion efficiency data. We found that although graphene layers incorporated in TiO₂ photoanode slightly decreased dye adsorption, they were able to significantly improve the electron transport, and the charge recombination at the interfaces of TiO₂/dye and TiO₂/electrolyte were greatly suppressed, leading to dramatic improvement in power conversion efficiency. When inserting three layers of pure graphene into the TiO₂ photoanode, high efficiency of 8.9% was obtained, constituting an over 23.6% improvement. Further increasing graphene layers to five, although electron lifetimes is the longest, both the largest charge transfer resistance and the least amount of the dye loading lead to the lowest device efficiency. Our work demonstrated, that pure graphene layer can be successfully incorporated into TiO₂ photoanode by E-spray method with easiness of thickness control and the photoanode with graphene/TiO₂ alternatively layered structure is an excellent candidate for DSSCs.     

Blocking layer optimisation of poly(3-hexylthiopene) based Solid State Dye Sensitized Solar Cells

The optimisation study of the fabrication of a compact TiO₂ blocking layer (via Spray Pyrolysis Deposition) for poly(3-hexylthiopene) (P3HT) for Solid State Dye Sensitized Solar Cells (SDSCs) is reported. We used a novel spray TiO₂ precursor solution composition obtained by adding acetylacetone to a conventional formulation (Diisopropoxytitanium bis(acetylacetonate) in ethanol). By Scanning Electron Microscopy a TiO₂ layer with compact morphology and thickness of around 100 nm is shown. Through a Tafel plot analysis an enhancement of the device diode-like behaviour induced by the acetylacetone blocking layer respect to the conventional one is observed. Significantly, the device fabricated with the acetylacetone blocking layer shows an overall increment of the cell performance with respect to the cell with the conventional one (ΔJ_sc/J_sc = +13.8%, ΔFF/FF = +39.7%, ΔPCE/PCE = +55.6%). A conversion efficiency optimum is found for 15 successive spray cycles where the diode-like behaviour of the acetylacetone blocking layer is more effective. Over three batches of cells (fabricated with P3HT and dye D35) an average conversion efficiency value of 3.9% (under a class A sun simulator with 1 sun A.M. 1.5 illumination conditions) was measured. From the best cell we fabricated a conversion efficiency value of 4.5% was extracted. This represents a significant increment with respect to previously reported values for P3HT/dye D35 based SDSCs.     

Theoretical study on novel double donor-based dyes used in high efficient dye-sensitized solar cells: The application of TDDFT study to the electron injection process

The geometries and electronic structures of organic dye sensitizers, CCT1A, CCT2A, CCT3A, CCT1PA, and CCT2PA comprising double-donor groups, π-spacer, and acceptor group forming D–D–π–A system, were studied using DFT and TDDFT. The calculated results have shown that TDDFT calculation using a newly-designed functional which takes into long-range interaction, CAM-B3LYP, was reasonably capable of predicting the excitation energies and the absorption spectra of the molecules. The adsorption of these dyes on the TiO₂ anatase (1 0 1) surface and the electron injection mechanism were also investigated using a dye-(TiO₂)₃₈ cluster model, employing PBE and TD-CAM-B3LYP calculations, respectively. The adsorption energy (E_ads) of CCTnA (n = 1–3) was calculated to be ?15.26, ?18.93, and ?20.12 kcal/mol respectively, indicating strong adsorption of dye to a TiO₂ surface by carboxylate groups. These calculated results suggested that the CCT3A is a promising candidate for highly efficient DSSCs. It was shown that the electron injection mechanism occurs by direct charge-transfer transition in a dye-TiO₂ interacting system, resulted in the stronger electronic coupling strengths of the anchoring group of the dyes and the TiO₂ surface which corresponded to higher observed J_sc as expected in CCT3A dye. Through a combined theoretical and experimental investigation we have shown that the trend of charge-injection efficiency in dye-sensitized solar cells constituted from dyes is determined by the adsorption energy of dye-(TiO₂)₃₈ complexes.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

High-performing transparent photodetectors based on Schottky contacts

Transparent UV-photodetectors exhibiting very high responsivity and fast operation are discussed. Schottky contact photoelectric devices utilizing wide band gap TiO₂ absorber layer were evaluated for their performances as UV-photodetectors. Three different work function metals Cu, Mo and Ni were used to realize Schottky barrier with TiO₂. Ni Schottky contacts were found to be most suitable to fabricate high responsivity (2.034 A/W) photodetector with faster rise time (0.14 ms) and wide linear dynamic range (128 dB) operating at small applied reverse bias of −1 V. However, higher barrier height in the case of Mo/TiO₂ interface resulted in lowest dark current density of the value 2.21×10⁻⁸ A/cm² with quick fall time of 0.52 ms. The modulation of the barrier height would provide a route for designing fast and high responsive Schottky photodetector with broad linear dynamic range performance.     

Stepwise co-sensitization as a useful tool for enhancement of power conversion efficiency of dye-sensitized solar cells: The case of an unsymmetrical porphyrin dyad and a metal-free organic dye

A tertiary arylamine compound (DC), which contains a terminal cyano-acetic group in one of its aryl groups, and an unsymmetrical porphyrin dyad of the type Zn[Porph]-L-H₂[Porph] (ZnP-H₂P), where Zn[Porph] and H₂[Porph] are metallated and free-base porphyrin units, respectively, and L is a bridging triazine group functionalized with a glycine moiety, and were synthesized and used for the fabrication of co-sensitized dye-sensitized solar cells (DSSCs). The photophysical and electronic properties of the two compounds revealed spectral absorption features and frontier orbital energy levels that are appropriate for use in DSSCs. Following a stepwise co-sensitization procedure, by immersing the TiO₂ electrode in separate solutions of the dyes in different sequence, two co-sensitized solar cells were obtained: devices C (ZnP-H₂P/DC) and D (DC/ZnP-H₂P).The two solar cells were found to exhibit power conversion efficiencies (PCEs) of 6.16% and 4.80%, respectively. The higher PCE value of device C, which is also higher than that of the individually sensitized devices based on the ZnP-H₂P and DC dyes, is attributed to enhanced photovoltaic parameters, i.e. short circuit current (J_sc = 11.72 mA/cm²), open circuit voltage (V_oc = 0.72 V), fill factor (FF = 0.73), as it is revealed by photovoltaic measurements (J–V curves) and by incident photon to current conversion efficiency (IPCE) spectra of the devices, and to a higher total dye loading. The overall performance of device C was further improved up to 7.68% (with J_sc = 13.45 mA/cm², V_oc = 0.76 V, and FF = 0.75), when a formic acid treated TiO₂ ZnP-H₂P co-sensitized photoanode was employed (device E). The increased PCE value of device E has been attributed to an enhanced J_sc value (=13.45 mA/cm²), which resulted from an increased dye loading, and an enhanced V_oc value (=0.76 V), attributed to an upward shift and increased of electron density in the TiO₂ CB. Furthermore, dark current and electrochemical impedance spectra (EIS) of device E revealed an enhanced electron transport rate in the formic acid treated TiO₂ photoanode, suppressed electron recombination at the photoanode/dye/electrolyte interface, as well as shorter electron transport time (τ_d), and longer electron lifetime (τ_e).     

Synthesis and some surface studies of laminated ZnO/TiO2 transparent bilayer by two-step growth

A laminated bilayer was prepared by first depositing titanium dioxide (TiO₂) nanocrystals on indium tin oxide (ITO) coated glass by a two-electrode cell. Zinc oxide (ZnO) thin film was thereafter deposited on the TiO₂ by two different techniques: electrochemical deposition and vacuum evaporation. The films were characterized by some surface probing techniques. Morphological study revealed that particle size of the TiO₂ underlayer increases between 110 and 138 nm with increase in deposition voltage. It also showed that ZnO thin film (overlayer) completely covered the underlying TiO₂ without chemical interaction between constituents of both layers. Cross-sectional FESEM study gave values of layered film thickness below 55 µm. Exhibition of strong diffraction peak at plane (121) indicated preference of TiO₂ film's growth orientation. It also suggested a feature of phase-pure brookite. Optical studies showed that each film exhibited strong absorption edge at λ=~330 nm and transmitted fairly across visible light region. Energy band gap lied between 3.24 and 3.43 eV. This study demonstrated successive layer deposition of transparent metal oxide structures from inorganic reagents. It also reaffirmed TiO₂ as a recipe for barrier layer that can hinder transition of holes from absorber to transparent front contact of nanostructured photonic devices.     

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.     

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.     

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.     

Nanotribological properties of ALD-processed bilayer TiO2/ZnO films

TiO₂/ZnO films grown by atomic layer deposition (ALD) demonstrated nanotribological behaviors using scratch testing. TEM profiles obtained an amorphous structure TiO₂ and nanocrystalline structure ZnO, whereas the sample has significant interface between the TiO₂/ZnO films. The experimental results show the relative XRD peak intensities are mainly contributed by a wurtzite oxide ZnO structure and no signal from the amorphous TiO₂.With respect to tribology, increased friction causes plastic deformation between the TiO₂ and ZnO films, in addition to delamination and particle loosening. The plastic deformation caused by adhesion and/or cohesion failure is reflected in the nanoscratch traces. The pile-up events at a loading penetration of 30 nm were measured at 21.8 μN for RT, 22.4 μN for 300 °C, and 36 μN for 400 °C. In comparison to the other conditions, the TiO₂/ZnO films annealed at 400 °C exhibited higher scratch resistance and friction with large debris, indicating the wear volume is reduced with increased annealing temperature and loading.