Efficient Performance of Electrostatic Spray-Deposited TiO2 Blocking Layers in Dye-Sensitized Solar Cells after Swift Heavy Ion Beam Irradiation

A compact TiO₂ layer (~1.1 μm) prepared by electrostatic spray deposition (ESD) and swift heavy ion beam (SHI) irradiation using oxygen ions onto a fluorinated tin oxide (FTO) conducting substrate showed enhancement of photovoltaic performance in dye-sensitized solar cells (DSSCs). The short circuit current density (J_sc = 12.2 mA cm^-2) of DSSCs was found to increase significantly when an ESD technique was applied for fabrication of the TiO₂ blocking layer, compared to a conventional spin-coated layer (J_sc = 8.9 mA cm^-2). When SHI irradiation of oxygen ions of fluence 1 × 10¹³ ions/cm² was carried out on the ESD TiO₂, it was found that the energy conversion efficiency improved mainly due to the increase in open circuit voltage of DSSCs. This increased energy conversion efficiency seems to be associated with improved electronic energy transfer by increasing the densification of the blocking layer and improving the adhesion between the blocking layer and the FTO substrate. The adhesion results from instantaneous local melting of the TiO₂ particles. An increase in the electron transport from the blocking layer may also retard the electron recombination process due to the oxidized species present in the electrolyte. These findings from novel treatments using ESD and SHI irradiation techniques may provide a new tool to improve the photovoltaic performance of DSSCs.     

The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO₂ nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO₂ DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO₂ electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO₂ nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6?wt.% rutile) TiO₂ nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3?mA?cm^?2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO₂ nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.     

An efficient and low-cost TiO2 compact layer for performance improvement of dye-sensitized solar cells

A TiO₂ organic sol was synthesised for the preparation of a compact TiO₂ layer on fluorine-doped tin oxide (FTO) glass by a dip-coating technique. The resultant thin film was used for the fabrication of dye-sensitized solar cells (DSSCs). The compact layer typically has a thickness of ca. 110 nm as indicated by its SEM, and consists of anatase as confirmed by the XRD pattern. Compared with the traditional DSSCs without this compact layer, the solar energy-to-electricity conversion efficiency, short-circuit current and open-circuit potential of the DSSCs with the compact layer were improved by 33.3%, 20.3%, and 10.2%, respectively. This can be attributed to the merits brought by the compact layer. It can effectively improve adherence of TiO₂ to FTO surface, provide a larger TiO₂/FTO contact area, and reduce the electron recombination by blocking the direct contact between the redox electrolyte and the conductive FTO surface.     

Ga-doped ZnO transparent electrodes with TiO<Subscript>2</Subscript> blocking layer/nanoparticles for dye-sensitized solar cells

Ga-doped ZnO [GZO] thin films were employed for the transparent electrodes in dye-sensitized solar cells [DSSCs]. The electrical property of the deposited GZO films was as good as that of commercially used fluorine-doped tin oxide [FTO]. In order to protect the GZO and enhance the photovoltaic properties, a TiO₂ blocking layer was deposited on the GZO surface. Then, TiO₂ nanoparticles were coated on the blocking layer, and dye was attached for the fabrication of DSSCs. The fabricated DSSCs with the GZO/TiO₂ glasses showed an enhanced conversion efficiency of 4.02% compared to the devices with the normal GZO glasses (3.36%). Furthermore, they showed better characteristics even than those using the FTO glasses, which can be attributed to the reduced charge recombination and series resistance.     

Enhancement of the photoelectric performance of dye-sensitized solar cells using Ag-doped TiO<Subscript>2</Subscript> nanofibers in a TiO<Subscript>2</Subscript> film as electrode

For high solar conversion efficiency of dye-sensitized solar cells [DSSCs], TiO₂ nanofiber [TN] and Ag-doped TiO₂ nanofiber [ATN] have been extended to be included in TiO₂ films to increase the amount of dye loading for a higher short-circuit current. The ATN was used on affected DSSCs to increase the open circuit voltage. This process had enhanced the exit in dye molecules which were rapidly split into electrons, and the DSSCs with ATN stop the recombination of the electronic process. The conversion efficiency of TiO₂ photoelectrode-based DSSCs was 4.74%; it was increased to 6.13% after adding 5 wt.% ATN into TiO₂ films. The electron lifetime of DSSCs with ATN increased from 0.29 to 0.34 s and that electron recombination was reduced.     

Influence of seed layer treatment on low temperature grown ZnO nanotubes: Performances in dye sensitized solar cells

Non-aligned and highly densely aligned ZnO nanotube (NTs), synthesized by low temperature solution method were applied as photoanode materials for the fabrication of efficient dye-sensitized solar cells (DSSCs). The crystalline and the morphological analysis revealed that the grown aligned ZnO NTs possessed a typical hexagonal crystal structure of outer and inner diameter ∼250 nm and ∼100 nm, respectively. ZnO seeding on FTO substrates is an essential step to achieve the aligned ZnO NTs. A DSSC fabricated with aligned ZnO NTs photoanode achieved high solar-to-electricity conversion efficiency of ∼2.2% with short circuit current (J_SC) of 5.5 mA/cm², open circuit voltage (V_OC) of 0.65 V and fill factor (FF) of 0.61. Significantly, the aligned ZnO NTs photoanode showed three times improved solar-to-electricity conversion efficiency than DSSC fabricated with non-aligned ZnO NTs. The enhanced performances were credited to the aligned morphology of ZnO NTs which executed the high charge collection and the transfer of electrons at the interfaces of ZnO NTs and electrolyte layer.     

Comparison on photocatalytic degradation of gaseous formaldehyde by TiO2, ZnO and their composite

In order to compare the photocatalytic properties of TiO₂, ZnO and their composite in the gas phase pollutant environment, nanocomposite with different mole ratios of TiO₂/ZnO were designed to degrade gaseous formaldehyde. The results showed that the rate constant of TiO₂ for formaldehyde degradation was 0.05 min^?1 which was two orders of magnitude larger than that of ZnO in our experiment. Through comprehensive analysis of UV–vis diffuse reflectance (UV–vis) spectra, photoluminescence spectra (PL) and energy band diagram, it was found that the differences of photocatalytic properties between ZnO and TiO₂ may mainly originate from the increased recombination of photoinduced charges in ZnO. The photocatalytic properties of TiO₂/ZnO composite for formaldehyde degradation were much worse than those of TiO₂, while better than those of ZnO. The addition of a small amount of ZnO weakened the photocatalytic properties of TiO₂. It may be attributed to that the recombination action of photoinduced electron–hole pairs in ZnO.     

Quasi solid state dye-sensitized solar cells with modified TiO2 photoelectrodes and triphenylamine-based dye

Quasi solid state dye-sensitized solar cells (DSSCs) have been fabricated with organic sol or TiCl₄ modified TiO₂ and porous TiO₂ photoanode and a triphenylamine-based dye (TPAR3) used as photosensitizer. Dark current measurements suggested that both modified TiO₂ photoelectrodes had significantly reduced the recombination rate of photoelectrons due to the reduced bare FTO surface in comparison to porous photoelectrode. The DSSC based on modified TiO₂ photoelectrodes showed improved photovoltaic parameters compared to the porous TiO₂ photoelectrode. The overall power conversion efficiency (PCE) is 3.27%, 4.73% and 6.8% for porous, TiCl₄ modified and sol modified TiO₂ photoelectrodes, respectively. The improved PCE with modified TiO₂ electrodes was attributed to the formation of a compact layer. This effectively improves adherence of TiO₂ to FTO surface, providing a larger TiO₂/FTO contact area and reducing the electron recombination by blocking the direct contact between redox electrolyte and the conductive FTO surface and enhances the electron collection efficiency.     

Improved photovoltage and performance by aminosilane-modified PEO/P(VDF-HFP) composite polymer electrolyte dye-sensitized solar cells

A PEO/P(VDF-HFP) composite polymer electrolyte was modified by different amounts of NH₂-end functional silane (3-amonopropyltriethoxysilane, APTS). Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were carried out to examine the configuration changes of the polymer electrolyte. The newly formed Si-O-Si network and interactions influenced the ionic conductivity of the APTS-modified polymer electrolyte and also enhanced the connection of the polymer electrolyte with the electrodes of the dye sensitized solar cells (DSSCs). The cyclic voltammograms and electrochemical impedance measurements indicated that the APTS deprotonated the TiO₂ photoanode surface and negatively changed the Fermi energy level and the conduction band edge to the vacuum level. This effectively reduced the interface recombination in the DSSC and improved the open circuit voltage. With moderate APTS content (0.1 M) modification, the DSSC exhibited a 58 mV improvement of photovoltage and an improved performance of 5.08% compared with 3.74% of the original DSSC.     

Structural,morphological, and optical studies of hydrothermally synthesized Nb-added TiO2 for DSSC application

Herein, titanium dioxide (TiO₂) nanoparticles doped with various concentrations (0–7 wt %) of niobium (Nb) are hydrothermally synthesized and used effectively as a photoelectrode for application in dye-sensitized solar cells (DSSCs). The rutile-to-anatase phase transition, accompanied by a change in crystallite size from 23.75 to 9.77 nm, is confirmed via X-ray diffraction (XRD) and Fourier transform (FT)-Raman spectroscopy. In addition, the prepared Nb–TiO₂ nanoparticles exhibit a spherical morphology with a mean grain diameter of 43.38–50.69 nm. Further, X-ray photoelectron spectroscopy (XPS) indicates a shift in the Fermi level of the TiO₂ towards the conduction band minimum, and an increase in the bandgap from 2.69 to 2.88 eV, with increasing Nb concentration. The resulting increases in the short-circuit current density (J_SC) and open circuit voltage (V_OC) with the increased injection and conductivity of electrons lead to the enhancement of the DSSC performance. EIS measurements represents the effect of Nb doping on charge transporting and recombination behavior of DSSCs. Moreover, the Nb–TiO₂-based DSSCs provide a better power conversion performance as compared to that of the pristine TiO₂.     

Electrodeposited nanoporous ZnO films exhibiting enhanced performance in dye-sensitized solar cells

Electrodeposition of nanoporous ZnO films and their applications to dye-sensitized solar cells (DSSCs) were investigated in the aim of developing cost-effective alternative synthetic methods and improving the ZnO-based DSSCs performance. ZnO films were grown by cathodic electrodeposition from an aqueous zinc nitrate solution containing polyvinylpyrrolidone (PVP) surfactant. PVP concentration had strong effects on the grain sizes and surface morphologies of ZnO films. Nanoporous ZnO film with grain size of 20-40 nm was obtained in the electrolyte containing 4 g/L PVP. The X-ray diffraction pattern showed that nanoporous ZnO films had a hexagonal wurtzite structure. Optical properties of such films were studied and the results indicated that the films had a band gap of 3.3 eV. DSSCs were fabricated from nanoporous ZnO films and the cell performance could be greatly improved with the increase of ZnO film thickness. The highest solar-to-electric energy conversion efficiency of 5.08% was obtained by using the electrodeposited double-layer ZnO films (8 μm thick nanoporous ZnO films on a 200 nm thick compact nanocrystalline ZnO film). The performance of such cell surpassed levels attained in previous studies on ZnO film-based DSSCs and was among the highest for DSSCs containing electrodeposited film components.     

Fabrication and photoelectrochemical properties of TiO2 films on Ti substrate for flexible dye-sensitized solar cells

The dye-sensitized solar cells (DSSCs) using Ti foil supporting substrate for fabricating nanocrystalline TiO₂ flexible film electrodes were developed, intending to improve the photoelectrochemical properties of flexible substrate-based DSSCs. The obtained cells were characterized by electrochemical impedance spectra (EIS), open circuit voltage decay (OCVD) measurement and Tafel plots. The experimental results indicate that the most important advantage of a Ti foil-based TiO₂ flexible electrode over a FTO glass-based electrode lies in its reduced sheet resistance, electron traps, and the retarded back reaction of electrons with tri-iodine ions in DSSCs. All above characteristics for the Ti substrate TiO₂ films are beneficial for decreasing the charge recombination in the TiO₂ electrode and prolonging the electron lifetimes for the DSSCs, as well as improvement of the overall solar conversion efficiency. The photocurrent of the cell fabricated with the Ti foil-based flexible electrode increased significantly, leading to a much higher overall solar conversion efficiency of 5.45% at 100 mW/cm² than the cell made with FTO glass-based TiO₂ electrodes. Above results demonstrate that Ti foil is a potential alternative to the conventional FTO glass substrate for the DSSCs.     

Symmetric electric double-layer capacitor containing imidazolium ionic liquid-based solid polymer electrolyte: Effect of TiO2 and ZnO nanoparticles on electrochemical behavior

Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF–HFP)-based polymer electrolytes embedded with 1-ethyl-3-methylimidazolium tetrafluoroborate ioniliquid have been synthesized to improve the ionic conductivity. Electric double-layer capacitors (EDLC) have been prepared using the synthesized polymer electrolytes. Inorganic oxide fillers (5 wt %) such as titanium dioxide (TiO₂) and zinc oxide (ZnO) nanoparticles have been added to polymer electrolytes to compare the electrochemical behavior of the fabricated EDLC. The intrinsic dielectric constant of nanoparticles contributes in ionic dissociation which enhances ionic conductivity of electrolytes and also controls the specific capacitance of the EDLC fabricated with these electrolytes. Physicochemical properties of polymer nanocomposites have been investigated using X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared analysis, which confirms decrease of crystalline phase in host polymer PVDF–HFP. The maximum voltage stability is obtained for TiO₂-based polymer electrolyte. The high specific capacitance as well as high energy density is obtained for the EDLC cell with TiO₂-based polymer electrolyte compared to EDLC with ZnO nanoparticles-based electrolyte. EDLC cells show specific capacitance of 76.4 and 44.51% of initial specific capacitance value at 2000th cycle for ZnO and TiO₂-based polymer electrolytes, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48757.     

Effect of TiO2 nanoparticle-accumulated bilayer photoelectrode and condenser lens-assisted solar concentrator on light harvesting in dye-sensitized solar cells

TiO₂ nanoparticles (NPs) with a size of 240 nm (T240), used as a light-scattering layer, were applied on 25-nm-sized TiO₂ NPs (T25) that were used as a dye-absorbing layer in the photoelectrodes of dye-sensitized solar cells (DSSCs). In addition, the incident light was concentrated via a condenser lens, and the effect of light concentration on the capacity of the light-scattering layer was systematically investigated. At the optimized focal length of the condenser lens, T25/T240 double layer (DL)-based DSSCs with the photoactive area of 0.36 cm² were found to have the short circuit current (I_sc) of 11.92 mA, the open circuit voltage (V_oc) of 0.74 V, and power conversion efficiency (PCE) of approximately 4.11%, which is significantly improved when they were compared to the T25 single layer (SL)-based DSSCs without using a solar concentrator (the corresponding values were the I_sc of 2.53 mA, the V_oc of 0.69, and the PCE of 3.57%). Thus, the use of the optimized light harvesting structure in the photoelectrodes of DSSCs in conjunction with light concentration was found to significantly enhance the power output of DSSCs.     

Double‐Layer Structure Photoanode with TiO2 Nanotubes and Nanoparticles for Dye‐Sensitized Solar Cells

Here, we report a novel double‐layer structure photoanode with TiO₂ nanotube (TNT) layer and TiO₂ nanoparticle (TP) layer via a two‐step method of electrochemical anodization and screen printing for dye‐sensitized solar cells (DSSCs). The results indicate that DSSCs with this double‐layer structure have significant advantages of large surface area, long electron lifetime, superior electron recombination restraint characteristics, and high light scattering. The layer thickness of nanotubes and nanoparticles is also investigated and finally an optimized double‐layer structure with excellent performance is prepared. With such a double‐layer structure photoanode, DSSC with a relative high conversion efficiency of 6.43% and a short‐circuit photocurrent density of 16.40 mA·cm^?2 is obtained.     

Improvement of the physical properties of ZnO/CdTe core-shell nanowire arrays by CdCl2 heat treatment for solar cells

CdTe is an important compound semiconductor for solar cells, and its use in nanowire-based heterostructures may become a critical requirement, owing to the potential scarcity of tellurium. The effects of the CdCl₂ heat treatment are investigated on the physical properties of vertically aligned ZnO/CdTe core-shell nanowire arrays grown by combining chemical bath deposition with close space sublimation. It is found that recrystallization phenomena are induced by the CdCl₂ heat treatment in the CdTe shell composed of nanograins: its crystallinity is improved while grain growth and texture randomization occur. The presence of a tellurium crystalline phase that may decorate grain boundaries is also revealed. The CdCl₂ heat treatment further favors the chlorine doping of the CdTe shell with the formation of chlorine A-centers and can result in the passivation of grain boundaries. The absorption properties of ZnO/CdTe core-shell nanowire arrays are highly efficient, and more than 80% of the incident light can be absorbed in the spectral range of the solar irradiance. The resulting photovoltaic properties of solar cells made from ZnO/CdTe core-shell nanowire arrays covered with CuSCN/Au back-side contact are also improved after the CdCl₂ heat treatment. However, recombination and trap phenomena are expected to operate, and the collection of the holes that are mainly photo-generated in the CdTe shell from the CuSCN/Au back-side contact is presumably identified as the main critical point in these solar cells.     

Optical and microstructural properties of ZnO/TiO2 nanolaminates prepared by atomic layer deposition

ZnO/TiO₂ nanolaminates were grown on Si (100) and quartz substrates by atomic layer deposition at 200°C using diethylzinc, titanium isopropoxide, and deionized water as precursors. All prepared multilayers are nominally 50 nm thick with a varying number of alternating TiO₂ and ZnO layers. Sample thickness and ellipsometric spectra were measured using a spectroscopic ellipsometer, and the parameters determined by computer simulation matched with the experimental results well. The effect of nanolaminate structure on the optical transmittance is investigated using an ultraviolet–visible-near-infrared spectrometer. The data from X-ray diffraction spectra suggest that layer growth appears to be substrate sensitive and film thickness also has an influence on the crystallization of films. High-resolution transmission electron microscopy images show clear lattice spacing of ZnO in nanolaminates, indicating that ZnO layers are polycrystalline with preferred (002) orientation while TiO₂ layers are amorphous.     

Bi2O3-sensitized hierarchically mesoporous ZnO nanoparticles for Hg(II) reduction

Herein, an affordable and novel approach to design Bi₂O₃-sensitized hierarchically mesoporous ZnO nanoparticles (NPs) with a variety of Bi₂O₃ contents is achieved for Hg(II) reduction upon visible light exposure. TEM images of both ZnO and 3% Bi₂O₃/ZnO samples exhibit nanoscale spherical-like structures with a regular shape and a particle size of ~30 nm. The incorporation of Bi₂O₃ on hierarchically mesoporous ZnO networks allows visible light to be harvested in a broad range, and the mesoporous 3% Bi₂O₃/ZnO heterostructure demonstrates the best photocatalytic efficiency for Hg(II) reduction with a value of ~100% after 60 min. The photoreduction rate over the 3% Bi₂O₃/ZnO heterostructure is enhanced 10 and 20 times more than that of TiO₂-P25 and ZnO NPs. The rate constant of the 3% Bi₂O₃/ZnO heterostructure is 16.8 and 33.6 fold larger than that of TiO₂-P25 and ZnO NPs. The superior Hg(II) photoreduction performance could be ascribed to the synergistic effect, excellent visible-light harvest, large surface area, and pore volume provided by incorporating Bi₂O₃ and the heterojunction design between p-type Bi₂O₃ and n-type ZnO. This alignment of the electronic bands provides charge carrier separation, thereby decreasing the recombination rate. Finally, the mechanisms and kinetics for the photocatalytic reduction of Hg(II) are proposed.     

Preparation and characterization of bipolar membranes modified using photocatalyst nano‐TiO2 and nano‐ZnO

The nano‐ZnO and nano‐TiO₂ were added into chitosan (CS) anion layer to prepare polyvinyl alcohol (PVA) ‐ sodium alginate (SA)/ TiO₂‐ZnO‐CS (here, PVA:polyvinyl alcohol; SA:sodium alginate) bipolar membrane (BPM), which was characterized using scanning electron microscopy, atomic force microscopy (AFM), thermogravimetric analysis (TG), electric universal testing machine, contact angle measurer, and so on. Experimental results showed that nano‐TiO₂‐ZnO exhibited better photocatalytic property for water splitting at the interlayer of BPM than nano‐TiO₂ or nano‐ZnO. The membrane impedance and voltage drop (IR drop) of the BPM were obviously decreased under the irradiation of high‐pressure mercury lamps. At a current density of 60 mA/cm², the cell voltage of PVA‐SA/TiO₂‐ZnO‐CS BPM‐equipped cell decreased by 1.0 V. And the cell voltages of PVA‐SA/TiO₂‐CS BPM‐equipped cell and PVA‐SA/ZnO‐CS BPM‐equipped cell were only reduced by 0.7 and 0.6 V, respectively. Furthermore, the hydrophilicity, thermal stability, and mechanical properties of the modified BPM were increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of ruthenium complex and its application in dye-sensitized solar cells

An amphiphilic bipyridyl ligand, 4,4′-dicarboxy-octyl-2,2′-bipyridine, and its ruthenium(□) complex (termed as S8) were synthesized and characterized by UV/Vis, IR and NMR spectroscopy. The performance of this S8 complex as charge transfer photo-sensitizer in TiO₂-based dye-sensitized solar cells was studied under standard AM 1.5 sunlight and by using an electrolyte consisting of 0.70 M 1,2-dimethyl-3-propyl-imidazolium iodide, 0.10 M LiI, 40 mM iodine and 0.125 M 4-tert-butylpyridine in acetonitrile. Aliphatic chains linking to carboxylate groups of S8 act as an effective electron donor and carboxylate groups act as an effective electron withdrawing between the TiO₂ layer and the carboxylate linking TiO₂ layer leading to increasing of electron density at this interface, which is attributed to increasing efficiency of electron injection to the TiO₂ conduction band from the excited state of dye. The complex, S8, gave a photocurrent density of 13.02 mA/cm², 0.60 V open circuit voltage and 0.69 fill factor yielding 5.36% efficiency. The S8 dye with aliphatic chain improved conversion efficiency of the resulting DSSCs compared with a cell fabricated using the N3 dye.