Growth of ZnO nanorods on TiO2 nanoparticles films and their application to the electrode of dye-sensitized solar cells

A ZnO nanorods (NRs)/TiO₂ nanoparticles (NPs) film has been prepared by electrochemical deposition of ZnO NRs growth on P25 TiO₂ NPs film surfaces. It was found that ZnO NRs/TiO₂ NPs could significantly improve the efficiency of dye-sensitized solar cells owing to its relatively enhanced light-scattering capability and efficient charge transport efficiency. The overall energy-conversion efficiency (η) of 3.48 % was achieved by the formation of ZnO NRs/TiO₂ NPs film, which is 33 % higher than that formed by TiO₂ NPs alone (η = 2.62 %). The charge recombination behavior of cells was investigated by electrochemical impedance spectra, and the results showed that ZnO NRs/TiO₂ NPs film has the longer electron lifetime than TiO₂ NPs alone, which could facilitate the reduction of recombination processes and thus would promote the photocatalysis and solar cell performance.     

Effects of HNO3 treatment of TiO2 nanoparticles on the photovoltaic properties of dye-sensitized solar cells

The effects of the nitric acid (HNO₃) treatment of TiO₂ nanoparticles on the photovoltaic properties of the dye-sensitized solar cell (DSSC) were investigated. The HNO₃ treatment enhanced the dispersion of TiO₂ particles, increased the surface area and porosity of the sintered TiO₂ films, increased the relative proportion of the Ti³⁺ state in the Ti 2p X-ray photoelectron spectroscopy spectrum, significantly increased the amount of adsorbed dye molecules on the TiO₂ electrode, and reduced the charge-transfer resistance at the TiO₂/dye/electrolyte interface. The short circuit photocurrent density (I_sc) was increased due to the increased amount of adsorbed dye molecules and the reduced charge-transfer resistance. The HNO₃ pre-treatment of TiO₂ particles improved the overall conversion efficiency of the DSSC by about 14%.     

The effects of the thickness of TiO2 films on the performance of dye-sensitized solar cells

Nanocrystalline anatase TiO₂ thin films with different thicknesses (0.5-2.0 μm) have been deposited on ITO-coated glass substrates by a sol-gel method and rapid thermal annealing for application as the work electrode for dye-sensitized solar cells (DSSC). From the results, the increases in thickness of TiO₂ films can increase adsorption of the N3 dye through TiO₂ layers to improve the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. However, the J_sc and V_oc of DSSC with a TiO₂ film thickness of 2.0 μm (8.5 mA/cm² and 0.61 V) are smaller than those of DSSC with a TiO₂ film thickness of 1.5 μm (9.2 mA/cm² and 0.62 V). It could be due to the fact that the increased thickness of TiO₂ thin films also resulted in a decrease in the transmittance of TiO₂ thin films thus reducing the incident light intensity on the N3 dye. An optimum power conversion efficiency (η) of 2.9% was obtained in a DSSC with the TiO₂ film thickness of 1.5 μm.     

Facile synthesis of highly branched jacks-like ZnO nanorods and their applications in dye-sensitized solar cells

Highly branched, jacks-like ZnO nanorods architecture were explored as a photoanode in dye-sensitized solar cells, and their photovoltaic performance was compared with that of branch-free ZnO nanorods photoanodes. The highly branched network and large pores of the jacks-like ZnO nanorods electrodes enhances the charge transport, and electrolyte penetration. Thus, the jacks-like ZnO nanorods DSSCs render a higher conversion efficiency of η = 1.82% (V_oc = 0.59 V, J_sc = 5.52 mA cm⁻²) than that of the branch-free ZnO nanorods electrodes (η = 1.08%, V_oc = 0.49 V, J_sc = 4.02 mA cm⁻²). The incident photon-to-current conversion efficiency measurements reveal that the jacks-like ZnO nanorods DSSCs exhibit higher internal quantum efficiency (∼59.1%) than do the branch-free ZnO nanorods DSSC (∼52.5%). The charge transfer resistances at the ZnO/dye/electrolyte interfaces investigated using electrochemical impedance spectroscopy showed that the jacks-like ZnO nanorods DSSC had high charge transfer resistance and a slightly longer electron lifetime, thus improving the solar-cell performance.     

Synthesis of hierarchical nanoparticles-based ZnO spheres for their application as the light blocking layers in dye-sensitized solar cells

Three-dimensional nanoparticles-based ZnO hierarchical spheres (ZnO-HS) with strong light harvesting and dye loading abilities have been fabricated by a simple hydrothermal method in this paper. These ZnO-HS were designed as the overlayer for light blocking and applied to the dye-sensitized solar cells (DSSCs) based on bare ZnO nanoparticles (ZnO-NP) or TiO₂ nanoparticles (TiO₂-NP). The results show that the values of the short-circuit current density (J _sc) and the power conversion efficiency (η) have been heightened up to 12.6 mA cm^?2 and 3.40 % for the ZnO-NP/ZnO-HS double-layered DSSC, far higher than the bare ZnO-NP DSSC. However, another DSSC assembled by the TiO₂-NP/ZnO-HS double-layered film displays an adverse result for the decreasing of J _sc and η even though the ZnO-HS light blocking layer has been established on the TiO₂-NP film. According to the electrochemical impedance data compared between the ZnO-NP/ZnO-HS double-layered and TiO₂-NP/ZnO-HS double-layered DSSC, it is found that the former possesses less possibility for the occurrence of charge recombination and electronic loss, which is responsible for its better photovoltaic response.     

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.     

Effect on interfacial charge transfer resistance by hybrid co-sensitization in DSSC applications

TiO₂ nanoparticles were synthesized by hydrothermal process to prepare metal oxide based photoanode for dye sensitized solar cell (DSSC) fabrication. X-ray diffraction analysis indicates the formation of tetragonal TiO₂. High resolution transmission electron microscopy reveals the presence of agglomerated TiO₂ particles and the average particle size is found to be 14 nm. The UV–Visible absorption spectrum ensures the absorption maximum at 268 nm. The band gap energy of TiO₂ nanoparticles was found to be 3.3 eV which lies in the ultra-violet (UV) region. Impedance studies of TiO₂ nanoparticles show an increase in conductivity with an increase in bias voltage. In the present work, the UV active TiO₂ nanoparticles are employed for the fabrication of DSSC based on the hybrid co-sensitization of natural dye (Eugenia Jambolana) and organic dye (Eosin). The interfacial charge transfer resistance phenomena of the DSSC determined by electrochemical impedance spectroscopy is discussed in detail. Photovoltaic efficiency of 0.1377 % is achieved for the fabricated DSSC with co-sensitization of natural and organic dyes.     

Preparation and characterization of (100 − x) TiO<Subscript>2</Subscript> + (x)ZnO nanocomposites for dye-sensitized solar cells using <Emphasis Type="Italic">Beta vulgaris</Emphasis> and <Emphasis Type="Italic">Syzygium cumini</Emphasis> natural dye extract

The present paper attempts to report the preparation of TiO₂–ZnO nanocomposite photoanode materials for dye-sensitized solar cells (DSSC) and analyse the efficiency of DSSC with natural dyes. The structural and optical characteristics of the composites were studied by transmission electron microscopy, X-ray diffraction, field effective scanning electron microscopy, energy dispersive spectrometry, photoluminescence and absorption spectroscopy. The synthesized nanocomposites formed on FTO substrates are applied as photoanode in a dye-sensitized solar cell (DSC). The natural dyes extracted from Beta vulgaris (Beetroot) and Syzygium cumini (black plum) were used in the fabrication of DSSC. The solar cells’ photovoltaic performance in terms of short-circuit current, open circuit voltage, fill factor and energy conversion efficiency was tested with photocurrent density–voltage measurements. The evolution of the solar cells parameters is explored as a function of the photoanode and type of dye used in DSSC fabrication.The obtained results show that the efficiency of DSSC significantly changes with the addition of ZnO to TiO_2, while the Beta vulgaris dye has evidently shown higher photo sensitized performance compared to Syzygium cumini in the preparation of DSSC.     

Design and development of electronic- and micro-structures for multi-functional working electrodes in dye-sensitized solar cells

This paper outlines a new strategy to optimize the performance of electrodes in dye-sensitized solar cells (DSSCs), through the engineering of electronic structures in conjunction with the micro-structures of the devices. We propose a simple hydrolysis method for the fabrication of a family of quasi-core–shell TiO₂ (hydrolysis)/PbS composites for working electrodes. Measurements confirm a shift in absorption from the UV to visible range. We also measured cell performance, including short-circuit photocurrent, open-circuit photovoltage, and the power conversion efficiency (η) of DSSCs. The obtained η of DSSC (6.05%) with a TiO₂ (P-25)/TiO₂ (hydrolysis) + 0.005 M PbS electrode is substantially higher than that of the conventional DSSC (5.11%) with a TiO₂ (P-25) electrode, due to improved p–n junctions, light-scattering, and light absorption. Finally, the shell of TiO₂ (hydrolysis) protected the core of PbS from the corrosive effects of electrolytes, thereby prolonging the life span of the DSSC. This novel approach to electrode design could lead to advances in DSSC as well as other energy applications including photo-catalysis technology.     

Enhanced photovoltaic performance of a dye sensitized solar cell with Cu/N Co-doped TiO<Subscript>2</Subscript> nanoparticles

Pure and Copper/Nitrogen (Cu/N)-codoped TiO₂ photoanodes with various Cu concentrations are prepared via sol–gel route for the photoanode application in dye-sensitized solar cells (DSSCs). All the prepared samples are characterized by X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), UV–Vis spectroscopy (UV–VIS) and Electrochemical Impedance Spectroscopy (EIS). Addition of suitable amount of Cu and N content in TiO₂ can alter its optical and electrical properties by extending absorption in the visible region and band gap reduction. The results show that some of the Ti sites are replaced by Cu atoms while O sites are occupied by N atoms. Upon adequate addition of Cu/N could lead to smaller particle size, higher specific surface area, increased dye adsorption and retarded charge carrier recombination. A significant improvement in the power conversion efficiency is observed in case of optimized 0.3 mol% Cu/N-doped TiO₂ nanoparticles (NPs) based DSSC. This optimized 0.3 mol% Cu/N-doped photoanode accomplished a best power conversion efficiency of 11.70% with a short circuit current density of 23.41 mA cm^?2 which is 41% higher than that of the pure TiO₂ photoanode based DSSC (6.82%).     

Fabrication and properties of meso-macroporous electrodes screen-printed from mesoporous titania nanoparticles for dye-sensitized solar cells

A meso-macroporous TiO₂ film electrode was fabricated by using mesoporous TiO₂ (m-TiO₂) nanoparticles through a screen-printing technique in order to efficiently control the main fabrication step of dye-sensitized solar cells (DSSCs). The qualities of the screen-printed m-TiO₂ films were characterized by means of spectroscopy, electron microscopy, nitrogen adsorption–desorption and photoelectrochemical measurements. Under the optimal paste composition and printing conditions, the DSSC based on the meso-macroporous m-TiO₂ film electrode exhibits an energy conversion efficiency of 4.14%, which is improved by 1.70% in comparison with DSSC made with commercially available nonporous TiO₂ nanoparticles (P25, Degussa) electrode printed with a similar paste composition. The meso-macroporous structure within the m-TiO₂ film is of great benefit to the dye adsorption, light absorption and the electrolyte transportation, and then to the improvement of the overall energy conversion efficiency of DSSC.     

Low-cost quasi-solid-state dye-sensitized solar cells based on a metal-free organic dye and a carbon aerogel counter electrode

Low-cost quasi-solid-state dye-sensitized solar cells (DSSCs) are designed and fabricated by using a metal-free organic dye and a mesoporous carbon aerogel instead of expensive ruthenium-based sensitizers and Pt electrode. The electrospun TiO₂ nanorods are added into a polyvinylidene fluoride (PVDF) solution to form a 3D network nanocomposite gel electrolyte. The presence of TiO₂ nanorods in the gel electrolyte obviously increases the ionic conductivity and decreases charge-transfer resistance of the DSSC. The effects of the gel electrolyte and the carbon aerogel counter electrode on electrochemical and photovoltaic properties have been investigated in detail. Particularly, an optimized DSSC with a nanocomposite gel electrolyte and a carbon aerogel counter electrode affords a power conversion efficiency (PCE) of 6.20% at a light intensity of 100 mW cm⁻².     

Alkyl and fluoro-alkyl substituted squaraine dyes: A prospective approach towards development of novel NIR sensitizers

Alkyl and fluoroalkyl substituted symmetrical and unsymmetrical squaraine dyes have been synthesized for the fabrication of dye-sensitized solar cells (DSSC) based on nanoporous TiO₂. Results of DSSC performance clearly indicate that introduction of molecular asymmetry and increase in the alkyl chain length of the squaraine sensitizers leads to the enhancement in the photovoltaic performance. A perusal of photo-action spectra of squaraine sensitizer corroborates that introduction of molecular asymmetry and fluoroalkyl substitution leads to hampering of blue-shifted H-aggregate formation. Estimation of energy of HOMO and LUMO for these squaraine sensitizers used in the present investigation indicates that about 0.16 eV is sufficient for electron injection from photoexcited dye to TiO₂ conduction band and dye regeneration.     

Synthesis of anatase TiO2 microspheres and their efficient performance in dye-sensitized solar cell

Nanomaterials play important role in performance of dye-sensitized solar cells. In this paper, highly phase pure anatase TiO₂ microspheres were synthesized using a low-cost hydrothermal route. Initially, X-ray diffraction studies and Raman spectroscopic analysis were carried out, and the formation of tetragonal structure of TiO₂ with the anatase phase was confirmed. The UV–Vis DRS studies showed the excellent reflectance and optical band-gap energy of 3.29 eV. The well-interconnected spherical nanoparticles with different sizes were examined by Field Emission Scanning Electron Microscopic analysis. The fabricated dye-sensitized solar cell (DSSC) composed of prepared TiO₂ microspheres as photoanode exhibited a higher power conversion efficiency (PCE) (η) of 5.4% as compared to commercial P25 with PCE of 3.6%. The higher J_sc (12.03 mA/cm²) in the fabricated DSSC due to efficient dye loading capacity and high light-scattering property was also observed.

     

Synthesis of cluster like TiO<Subscript>2</Subscript> mesoporous spheres and nanorods and their applications in dye-sensitized solar cells

Cluster like mesoporous TiO₂ spheres, nanorods and nanoparticles were synthesized by simple wet chemical method. The TiO₂ mesoporous spheres, nanorods and nanoparticles were characterized by powder X-ray diffraction, Raman spectroscopy, ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy and transmission electron microscopy. Accordingly, a possible growth mechanism of mesoporous spheres, nanorods and nanoparticles were discussed. The changes of the dye-sensitized solar cell (DSSC) performance with the variation of the nanostructures of TiO₂ which were used in photoanodes have been investigated. The TiO₂ mesoporous sphere based DSSC with the film thickness of 20 μm was assembled and a conversion efficiency of 6.69% was obtained.     

Effect of atomic layer deposited ultra thin HfO2 and Al2O3 interfacial layers on the performance of dye sensitized solar cells

The objective of this work was to investigate the improvement in performance of dye sensitized solar cells (DSSCs) by depositing ultra thin metal oxides (hafnium oxide (HfO₂) and aluminum oxide (Al₂O₃)) on mesoporous TiO₂ photoelectrode using atomic layer deposition (ALD) method. Different thicknesses of HfO₂ and Al₂O₃ layers (5, 10 and 20 ALD cycles) were deposited on the mesoporous TiO₂ surface prior to dye loading process used for fabrication of DSSCs. It was observed that the ALD deposition of ultrathin oxides significantly improved the performance of DSSCs and that the improvement in the DSSC performance depends on the thickness of the deposited HfO₂ and Al₂O₃ films. Compared to a reference DSSC the incorporation of a HfO₂ layer resulted in 69% improvement (from 4.2 to 7.1%) in the efficiency of the cell and incorporation of Al₂O₃ (20 cycles) resulted in 19% improvement (from 4.2 to 5.0%) in the efficiency of the cell. These results suggest that ultrathin metal oxide layers affect the density and the distribution of interface states at the TiO₂/organic dye and TiO₂/liquid electrolyte interfaces and hence can be utilized to treat these interfaces in DSSCs.     

Development of a new solid-state absorber material for dye-sensitized solar cell (DSSC)

In contrast to the conventional DSSC systems, where the dye molecules are used as light harvesting material, here a solid-state absorber was used as a sensitizer in conjunction with the dye. The materials like ZnO and Al₂O₃ : C, which will show optically stimulated luminescence (OSL) upon irradiation were used as extremely thin absorber layers. This novel architecture allows broader spectral absorption, an increase in photocurrent, and hence, an improved efficiency because of the mobility of the trapped electrons in the absorber material after irradiation, to the TiO₂ conduction band. Nanocrystalline mesoporous TiO₂ photoanodes were fabricated using these solid-state absorber materials and after irradiation, a few number of samples were co-sensitized with N719 dye. On comparing both the dye loaded photoanodes (ZnO/TiO₂ and Al₂O₃ : C/TiO₂), it can be concluded from the present studies that, the Al₂O₃ : C is superior to ZnO under photon irradiation. Al₂O₃ : C is more sensitive to photon irradiation than ZnO and hence there can be more trap centres produced in Al₂O₃ : C.     

The optical properties of nanoporous structured titanium dioxide and the photovoltaic efficiency on DSSC

This study examined the characterization of nanoporous structured titanium dioxide and its application to dye-sensitized solar cells (DSSCs). TEM revealed nanopore sizes of 10.0 nm with a regular hexagonal form. When nanoporous structured TiO₂ was applied to DSSC, the energy conversion efficiency was enhanced considerably compared with that using nanometer sized TiO₂ prepared using a hydrothermal method. The energy conversion efficiency of the DSSC prepared from nanoporous structured TiO₂ was approximately 8.71% with the N719 dye under 100 mW cm⁻² simulated light. FT-IR spectroscopy showed that the dye molecules were attached perfectly to the surface and more dye molecules were absorbed on the nanoporous structured TiO₂ than on the nano-sized TiO₂ particles prepared using a conventional hydrothermal method. Electrostatic force microscopy (EFM) showed that the electrons were transferred rapidly to the surface of the nanoporous structured TiO₂ film.     

LiFePO<Subscript>4</Subscript>/TiO<Subscript>2</Subscript>/Pt composite film used as effective and robust counter electrode for dye sensitized solar cells

A series of composite films based on LiFePO₄/TiO₂/Pt were synthesized and used as counter electrodes for dye sensitized solar cells (DSSCs). The composites are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET). These analysis results demonstrate that the crystal structure of LiFePO₄ in composite is not changed, and the prepared LiFePO₄/TiO₂/Pt composite films hold a rough surface and porous structure which provide more catalytic activity sites for I₃ ^? reduction and more space for I^?/I₃ ^? diffusion. The DSSC based on LiFePO₄/TiO₂/Pt composite CEs shows a high power conversion efficiency of 6.23% at a low Pt dosage of 2%, comparable to the conventional magnetron sputtering Pt CE (6.31%). The electrochemical analysis reveals that the presented composite CEs have good electrocatalytic activity and low charge transfer resistance. Furthermore, the DSSCs based on LiFePO₄/TiO₂/Pt composite CE exhibit high stability under the continuous tests condition and electrolyte soaking. The results suggest that this LiFePO₄-based composite film could be a perspective electrode for practical application of DSSCs and it maybe provide a potential for further research about photo-charging lithium-ion batteries.     

Novel construction of CdS-encapsulated TiO2 nano test tubes corked with ZnO nanorods

A novel TiO₂ nanotube array/CdS nanoparticle/ZnO nanorod (TiO₂ NT/CdS/ZnO NR) photocatalyst was constructed by chemical assembling CdS into the TiO₂ NTs, and then laying ZnO NRs on the surface. The SEM results showed that the TiO₂ NTs looked like many “nano test tubes” and the ZnO NRs served as the corks to seal the nozzle. This photocatalyst exhibited a wide absorption range (200-535 nm) in both ultraviolet and visible regions (UV-vis region), and maintained very high photoelectrocatalytic (PEC) activities. The maximum photoelectric conversion efficiencies (η) of TiO₂ NT/CdS/ZnO NRs are 31.8 and 5.98% under UV light (365 nm) and visible light (420-800 nm), respectively.