The Effects of Co-Sensitization and Electronic Structure of Nanocrystalline N/TiO<Subscript>2</Subscript> Anode on the Performance of Dye-Sensitized Solar Cells

N/TiO₂ nanocrystalline film anodes were obtained by doping nonmetallic element N which could change the LUMO of anode. This paper also studied the match between the LUMO energy lever of N/TiO₂ anode and the dye, which led to the easy injection of electron from the excited state of dye molecule to the conduction band of semiconductor, and thus improved the photoelectric conversion efficiency and reduced the impedance of solar cells. The solar cell based on N/TiO₂ anode film co-sensitized by P3HT (poly(3-hexylthiophene))/N719(RuL2(NCS)2:2TBA (L = 2,2′-bipyridyl-4,4′-dicarboxylic acid)), the absorption region of which covered the entire visible region in solar cells, showed a short-circuit current density of 6.88 mA cm⁻², an open-circuit voltage of 0.616 V, and a photoelectric conversion efficiency of 2.34%.     

Recent progress in electrospinning TiO2 nanostructured photo‐anode of dye‐sensitized solar cells

The key to improving the performance of dye‐sensitized solar cells is the photo‐anode that has much dye adsorption and short optoelectronic transmission path. Electrospun TiO₂ films in photo‐anode have high specific surface area and meet the demand exactly. The article summarizes these efforts in TiO₂ photo‐anode improvement, including various morphology, different one‐dimensional and two‐dimensional composite structure, and varied element doped TiO₂ photo‐anode. Besides, the review makes comparison with these different TiO₂ photo‐anodes in photoelectric properties. The conclusions provide a clear guidance in design of morphology, structure, and doping, which is helpful for researcher to improve the performance of the anode and increase the photoelectric conversion efficiency especially those prepared using electrospinning. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45649.     

Optimization of the dye-sensitized solar cell performance by mechanical compression

In this study, the P25 titanium dioxide (TiO₂) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO₂ NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO₂ inter-particle distance improving the electron transport efficiency. The UV–vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO₂ NP thin film compressed at pressure of 279 kg/cm², the minimum resistance of 9.38 Ω at dye/TiO₂ NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm², and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO₂ NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.     

Fabrication of Three-Dimensionally Ordered Macroporous TiO2 Films with Enhanced Photovoltaic Conversion Efficiency

Negative-charged polystyrene (PS) microspheres were prepared through a soap-free emulsion polymerization method using potassium persulfate as initiator. Three-dimensionally ordered macroporous TiO₂ films were fabricated using the high-quality PS colloidal crystals templates obtained via a horizontal deposition method. The as-prepared macroporous TiO₂ films were applied as the photoanodes in dye-sensitized solar cell (DSSC). The microstructure of the products were characterized by X-ray diffractometer, fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption–desorption analyzer. The results showed that the macroporous TiO₂ films replicated well the 3D ordered structure derived from PS colloidal crystal templates and revealed a relatively large specific surface area (69.99 m²/g), which could increase the capacity of TiO₂ film anode for absorbing dyes and scattering light. The photocurrent–voltage (I–V) characteristics of DSSC were measured by a digital source meter under simulated solar light. The results indicated that the introduction of an ordered macroporous TiO₂ interfacial layer increased the photovoltaic conversion efficiency, which was improved by 68 % from 3.61 to 6.08 %, as compared to a device using a bare P25 TiO₂ photoanode. Our results showed that the hierarchically ordered macroporous TiO₂ bilayer films photoanode for DSSC could be helpful to improve the photovoltaic conversion efficiency.     

Fabrication of morphology controllable rutile TiO2 nanowire arrays by solvothermal route for dye-sensitized solar cells

Highly ordered, vertically oriented TiO₂ nanowire arrays (TNAs) are synthesized directly on transparent conducting substrate by solvothermal procedure without any template. The X-ray diffraction (XRD) pattern shows that TiO₂ array is in rutile phase growing along the (0 0 2) direction. The field-emission scanning electron microscopy (FE-SEM) images of the samples indicate that the TiO₂ array surface morphology and orientation are highly dependent on the synthesis conditions. In a typical condition of solvothermal at 180 °C for 2 h, the TNAs are composed of nanowires 10 ± 2 nm in width, and several nanowires bunch together to form a larger secondary structure of 60 ± 10 nm wide. Dye-sensitized solar cell (DSSC) assembled with the TNAs grown on the FTO glass as photoanode under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) achieves an overall photoelectric conversion efficiency of 1.64%.     

Study on the Performance of Zn,N/TiO<Subscript>2</Subscript> Anode Film and Co-Sensitization in DSSC

Zn,N-TiO₂ powder was prepared using TiCl₄ as the precursor. XRD, TEM and CV characterizations show Zn,N have been doped into nano-crystal TiO₂ successfully, and the absorbance range of TiO₂ anode red-shift to the visible region. Zn,N doped-TiO₂ anode film was first prepared by combined technology. Ultraviolet–Visible (UV–Vis) chararterization proved there is a complementarity in UV–Vis absorbance range between poly (3-dodecylthiophene) (P3DDT) and N719. Solar cell based on Zn,N-TiO₂ was first co-sensitized by P3DDT and N719. A solar-to-electric energy conversion efficiency of 3.25% was attained with the system. The photoelectric conversion efficiency, V_oc and J_sc have been all increased compare to the single dye-sensitized solar cell.     

Mesoporous TiO<Subscript>2</Subscript> microspheres synthesized via a facile hydrothermal method for dye sensitized solar cell applications

Mesoporous TiO₂ microspheres were successfully synthesized by a facile hydrothermal process and the obtained product was sintered at 450 °C. The sintered TiO₂ powder was characterised by powder X-ray diffraction pattern and the result shows pure anatase phase with good crystalline nature. The morphological image of field emission scanning electron microscopy and high resolution transmission electron microscopy shows spherical shape and size of the particles is around 100 to 300 nm. The Brunauer–Emmett–Teller surface area of synthesized TiO₂ material was 56.32 m² g^?1 and average pore width of synthesized materials was 7.1 and 9.3 nm. Bimodal pore structure of TiO₂ microspheres has been very effective for electrolyte diffusion into photoanode in dye sensitized solar cells. The synthesized anatase TiO₂ microsphere based dye sensitized solar cells have high surface area with light scattering effect to enhance the photocurrent and conversion efficiency than the commercial P25 photoanode material. The power conversion efficiency of synthesized mesoporous TiO₂ microspheres and commercial P25 material is 4.2 and 2.7 % respectively. Therefore bimodal mesoporous anatase TiO₂ microsphere appears to be a promising and potential candidate for dye sensitized solar cells (DSSC) application.     

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.     

Flexible photoanodes of TiO2 particles and metallic single-walled carbon nanotubes for flexible dye-sensitized solar cells

Recent advance in flexible electronics demands development of flexible energy sources. Of particular interests are flexible dye-sensitized solar cells (DSCs). However, a brittle nature of TiO₂ materials is one of hurdles to realize flexible DSCs. Here we synthesized flexible photoanodes of TiO₂ particles and single-walled carbon nanotubes (SWNTs). Metallic SWNTs provided a greater photovoltaic conversion efficiency than semiconducting SWNTs due to the more efficient electron transport. The metallic SWNTs also constructed effective mechanical network among TiO₂ particles providing flexibility and durability. The photoanode was transferred on an indium tin oxide (ITO)-coated polyethylene terephthalate film and characterized for front-illuminated DSCs under the AM 1.5 simulated sunlight. There was only a small decrease in photovoltaic conversion efficiency with bending which was primarily caused by cracking of the ITO layer. Due to this limitation, the TiO₂–metallic SWNT photoanode was transferred on a Ti foil and went through up to 1000 bending cycles. The cycled photoanode was assembled for back-illuminated DSCs due to the non-transparent Ti foil. There was no decrease in photovoltaic conversion efficiency even after 1000 bending cycles demonstrating excellent flexibility and durability.     

Au Nanoparticles as Interfacial Layer for CdS Quantum Dot-sensitized Solar Cells

Quantum dot-sensitized solar cells based on fluorine-doped tin oxide (FTO)/Au/TiO₂/CdS photoanode and polysulfide electrolyte are fabricated. Au nanoparticles (NPs) as interfacial layer between FTO and TiO₂ layer are dip-coated on FTO surface. The structure, morphology and impedance of the photoanodes and the photovoltaic performance of the cells are investigated. A power conversion efficiency of 1.62% has been obtained for FTO/Au/TiO₂/CdS cell, which is about 88% higher than that for FTO/TiO₂/CdS cell (0.86%). The easier transport of excited electron and the suppression of charge recombination in the photoanode due to the introduction of Au NP layer should be responsible for the performance enhancement of the cell.     

Incorporation of plasma-functionalized carbon nanocapsules into a nanocrystalline TiO2 photoanode for use in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were fabricated using TiO₂ nanoparticles incorporating different amounts of plasma functionalized carbon nanocapsules (CNCs) as the photoanode. The functionalization was obtained by grafting maleic anhydride (MA) onto the walls of CNCs immediately after the in situ argon plasma treatment. Nanocrystalline semiconductor film electrodes were prepared by sintering TiO₂ with added MA-CNCs on a conducting glass substrate. Capacitance measurements obtained from electrochemical impedance spectroscopy (EIS) analysis in an aqueous electrolyte are fitted using the Mott–Schottky relationship and demonstrate the variation of flatband potential (V_fb) for the composite with MA-CNC content. The potential chronoamperometric and cyclic voltammetric data supports the argument that the increased V_fb minimizes the defect state for trapping/detrapping of electrons within the MA-CNC/TiO₂. As a result of higher film capacitance and electron accumulation, the MA-CNC/TiO₂ shows increased conversion efficiency and photocurrent density when used as the photoanode in DSSCs. EIS measurement further demonstrates that charge recombination at the interface of MA-CNC/TiO₂ and electrolyte is suppressed with increasing electron lifetime and is in good agreement with the photovoltaic performance. The amount of MA-CNCs added, however needs to be optimized due to the unavoidable issue of aggregation.     

Enhanced photoelectric efficiency by surface modification of TiO<Subscript>2</Subscript> thin film using various acidic species

This study examined the photoelectric conversion efficiency of the dye-sensitized solar cell (DSSC) when the surface of a nanometer-sized TiO₂ film, which was prepared using the solvothermal method, was modified by five acid compounds. The TiO₂ film exhibited an anatase structure with an average particle size in the range of 10–15 nm, and the maximum absorption band was shown in the UV-visible spectrum around 360 nm. The surface colors of the carboxylic acid-modified TiO₂ films were changed to light or dark with differing energy conversion efficiencies. Particularly, the conversion efficiency was considerably enhanced from approximately 6.25% for the non-modified TiO₂ film to approximately 7.50% for the film treated by acetic acid of 1.0 mole, with the N719 dye under 100 mW/cm² of simulated sunlight. FT-IR analysis of the films after N719 dye adsorption confirmed that the IR spectrum of the modified TiO₂ showed a sharp and strong band at 500 cm⁻¹, which was assigned to a metal-O bond, due to the formation of a new Ti-O bond between the O of COO⁻ and the Ti atom, which was relatively weaker in the non-modified TiO₂. Furthermore, these results were in agreement with an electrostatic force microscopy (EFM) study showing that the electrons were transferred rapidly to the surface of the acetic acid-modified TiO₂ film, compared with that on the nonmodified TiO₂ film.     

Effect of silver (Ag) ions irradiation on the structural,optical and photovoltaic properties of Mn doped TiO2 thin films based dye sensitized solar cells

Dye sensitized solar cell (DSSC) is an emerging energy harvesting tool which converts direct sunlight into electrical energy. These cells have much better properties in contrast with silicon based solar cells because of their flexible nature, light weight, low cost, environment friendly nature, and involvement of a simple manufacturing process. Since, a photoanode is the backbone of DSSC, we synthesized a pure and 1% manganese (Mn) doped titanium dioxide (TiO₂) films by sol-gel method which are irradiated with silver (Ag) ions at two different concentrations (2 × 10¹⁴ and 4 × 10¹⁴) ions-cm^?2. X-ray diffraction revealed that Mn doping followed by Ag irradiation transformed TiO₂ from pure anatase to rutile phase. Ultraviolet–visible spectroscopy exposed the reduction in band gap of TiO₂ film during this doping and irradiation process. Therefore, absorption is enhanced with red shift in UV-range. When these films are used as a photoanode in DSSC, 1% Mn doped TiO₂ film exposed with Ag at the concentration of (2 × 10¹⁴) ions-cm^?2 exhibited maximum efficiency of 2.40%.     

Titanium flexible photoanode consisting of an array of TiO2 nanotubes filled with a nanocomposite of TiO2 and graphite for dye-sensitized solar cells

A flexible dye-sensitized solar cell (DSSC) was fabricated using a photoanode consisting of an array of TiO₂ nanotubes (TNT) filled with a nanocomposite of TiO₂ (P90) and nanographite. The array of TNT was obtained by anodic oxidation of Ti foil, and this Ti foil with TNT was used as the photoanode of the DSSC. Each tube in the array has an average diameter of 100 nm. The morphologies of the array of TNT were obtained both after and before filling them with the TiO₂/graphite nanocomposite, using a field-emission scanning electron microscopy (FE-SEM). DSSC with photoanode consisting of the nanocomposite (photoanode designated as Graphite/P90-TNT) rendered a light-to-electricity conversion efficiency (η) of 5.75%. In contrast, the cells with photoanodes consisting of only TNT (photoanode designated as TNT) and TNT filled with P90-TiO₂ (photoanode designated as P90-TNT) exhibited efficiencies (η) of 4.44% and 5.14%, respectively. The enhancements in the η’s in favor of the cells with P90-TNT and Graphite/P90-TNT were attributed to the filled P90 and nanocomposite, respectively. The filled particles were assumed to provide more conductive pathways for electron transfer and prolonged lifetime for electrons in the film of TNT. The results were substantiated by light-absorption values, incident-photo-to-current efficiency (IPCE) curves, Nyquist and Bode plots of electrochemical impedance spectroscopy (EIS), and photopotential transient curves.     

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.     

Enhanced light scattering and photovoltaic performance for dye-sensitized solar cells by embedding submicron SiO2/TiO2 core/shell particles in photoanode

The introduction of light scattering in the photoanodes of dye-sensitized solar cells is one of the most effective approaches to enhance their photovoltaic performance. In this work, we prepared submicron SiO₂/TiO₂ core/shell particles and embedded these particles in the nanostructured TiO₂ photoanodes for light to scatter in the dye-sensitized solar cells. Due to the large difference in the refractive index between the SiO₂ core and the TiO₂ shell, the embedded submicron SiO₂/TiO₂ core/shell particles showed strong light scattering effect. Light absorbance of the dyed photoanode with the embedded SiO₂/TiO₂ particles for light scattering was found to be three times stronger than the one without light scattering particles over a wide wavelength range. The power conversion efficiency of dye-sensitized solar cells was increased by about 50% after the introduction of light scattering SiO₂/TiO₂ core/shell particles in the photoanode. This work will provide a base for further enhancement in the photovoltaic performance of dye-sensitized solar cells by optimizing the submicron SiO₂/TiO₂ core/shell particles and the photoanodes.     

Light management in dye-sensitized solar cell

Dye-sensitized solar cell (DSSC) is composed of a nanocrystalline TiO₂ film whose surface is covered with dye molecules, an iodide/tri-iodide electrolyte and a platinum counter electrode. Charge generation occurs when dye absorbs photon energy, which is separated by injection of photo-excited electrons into the conduction band of TiO₂. The photo-injected electrons are transported through TiO₂ network and collected at transparent conducting electrode. The oxidized dyes are regenerated by oxidation of iodide. Light-to-electricity conversion efficiency depends on photocurrent density, open-circuit voltage and fill factor. Photocurrent density is related to the incident photon-to-current conversion efficiency (IPCE) that is a collective measure of light harvesting, charge separation and charge collection efficiency. Since the higher IPCE, the higher photocurrent density becomes, light management in DSSC is one of most important issues. In this paper, effective methods to improve IPCE are described including size-dependent light scattering effect, bi-functionality design in material synthesis and panchromatic approach such as selective position of different dyes in a mesoporous TiO₂ film.     

Photovoltaic performance improvement of dye-sensitized solar cells based on tantalum-doped TiO2 thin films

Dye-sensitized solar cells based on a tantalum (Ta)-doped TiO₂ thin film prepared by the hydrothermal method show a photovoltaic efficiency of 8.18%, which is higher than that of the undoped TiO₂ thin film (7.40%). The Mott-Schottky plot indicates that the Ta-doped TiO₂ photoanode shifts the flat band potential positively and increases the electron density. The positive shift of the flat band potential improves the driving force of injected electrons from the LUMO of the dye to the conduction band of TiO₂. Furthermore, the increased electron density caused by the Ta-doped TiO₂ improves the fill factor of the solar cell. The increased electron density accelerates the transfer rate of electrons in the Ta-doped TiO₂ thin films by comparison to undoped films, which is confirmed by intensity-modulated photocurrent spectroscopy measurements.     

Effects of Eu3+ and Er3+ Doping on Photoelectrical Performance of Dye‐Sensitized Solar Cells

A novel tri‐layer film photoelectrode structure of DSSC by introducing Eu³⁺ and Er³⁺ ions into TiO₂ film was proposed. The photoelectric conversion efficiency of the DSSC with Er³⁺:TiO₂/Eu³⁺:TiO₂/TiO₂ tri‐layer electrode reaches 7.41%, increased by a factor of 1.44 compared to that of the DSSC without Eu³⁺ and Er³⁺ doping. The higher efficiency for DSSC with the tri‐layer electrode is mainly attributed to the down‐conversion luminescence effect by Eu³⁺ ions from ultraviolet light to visible light and up‐conversion luminescence effect by Er³⁺ ions from infrared light to visible light.     

All-solid-state quantum-dot-sensitized solar cells with compact PbS quantum-dot thin films and TiO2 nanorod arrays

To improve the electron injection efficiency from PbS quantum dots to TiO₂ nanorods and prevent the direct contact of spiro-OMeTAD and TiO₂ nanorods, a compact PbS quantum-dot thin film can be successfully obtained on TiO₂ nanorod arrays 360 nm in length by repeated spin coating of Pb(Ac)₂, Na₂S and 1,2-ethanedithiol solution in a step-by-step process. The corresponding solid-state quantum-dot-sensitized solar cells are fabricated using a novel structured FTO/compact PbS quantum-dot thin film sensitized TiO₂ nanorod array/spiro-OMeTAD/Au that achieves a photoelectric conversion efficiency of 3.57% under AM 1.5 G illumination (100 mW cm⁻²), which represents a high value among all-solid-state PbS quantum-dot-sensitized TiO₂ nanorod array solar cells.