Reduced graphene oxide–titania nanocomposite‐modified photoanode for efficient dye‐sensitized solar cells

We report the successful application of reduced graphene oxide–titania (rGO–TiO₂) nanocomposite as an efficient photoanode for dye‐sensitized solar cell (DSSC). The DSSC assembled with the rGO–TiO₂‐modified photoanode demonstrated an enhanced solar to electrical energy conversion efficiency of 4.74% compared with the photoanode of DSSC composed with unmodified TiO₂ (2.19%) under full sunlight illumination (100 mW/cm², AM 1.5G) as a result of the better charge collection efficiency of rGO, which reduced the back electron transfer process. Influence of the rGO content on the overall efficiency was also investigated, and the optimal rGO content for TiO₂ was 0.5 mg. Further, the modification of rGO–TiO₂ on the compact layer TiO₂ surface led to an increase in efficiency to 5.83%. The superior charge collection and enhanced solar energy conversion efficiency of the rGO–TiO₂ nanocomposite makes it to be used as a promising alternative to conventional photoanode‐based DSSCs. Copyright © 2015 John Wiley & Sons, Ltd.     

Solid-state dye-sensitized solar cell with p-type NiO as a hole collector

A solid-state dye-sensitized solar cells (DSSC) comprising of p-type NiO thin layer on TiO₂ was fabricated in which the dye is adsorbed on the p-type oxide and the thin NiO layer acts as a hole collector as well as a barrier for charge recombination. DSSC with NiO-coated TiO₂ electrodes with Ru-dye delivers I_sc=0.15 mA and V_oc=480 mV. It was shown that the p-type oxide materials could be successfully used to construct DSSC and the plausible charge transfer mechanism is discussed.     

Selective conditions for the fabrication of a flexible dye-sensitized solar cell with Ti/TiO2 photoanode

The effects of four factors, i.e., (i) sputter-deposition time of platinum (Pt) film, (ii) sintering temperature of TiO₂-coated Ti foil (Ti/TiO₂), (iii) thickness of Ti foil, and (iv) concentration of iodine are reported for the photovoltaic performance of a back-illuminated flexible dye-sensitized solar cell (DSSC) with Ti foil substrate for the TiO₂ layer. Optimization of these four factors yields a solar-to-electricity conversion efficiency (η) of 5.95%. Transmittance spectra, cyclic voltammetry (CV), electrochemical impedance spectra (EIS), X-ray diffraction (XRD), scanning electron micrographs (SEM), and laser-induced photovoltage transient technique are used to substantiate the explanations.     

Newly designed dye-sensitized solar cells fabricated with double-layered TiO2 (bottom layer)/Bx–TiO2 (top layer) combined electrodes for improved photocurrent

An unusual double-layered TiO₂ (bottom layer)/B_x–TiO₂ (top layer) combined electrode array was investigated to improve the photocurrent in dye-sensitized solar cells (DSSCs). A positive semiconductor, B_x–TiO₂, with nanometer-sized B (1.0, 5.0, and 10.0 mol%)-incorporated TiO₂ prepared using a solvothermal method, was utilized as the working electrode material by coating onto the second level above the TiO₂ electrode. The photocurrent and photovoltaic efficiency of the TiO₂ (bottom)/B_x–TiO₂ (top)-DSSC were 20.5% and 17.3% greater, respectively, than that of the double-layers of anatase TiO₂–DSSC in the photocurrent–voltage (I–V) curve of the optimal electrode. This result was attributed to their energy levels of reduction (LUMO)/oxidation (HOMO) as determined by cyclic voltammetry (CV). As the LUMO level of B_x–TiO₂ was located at a slightly higher level than that of pure anatase TiO₂, the electrons donated from the dye were easily transferred to the surface of the TiO₂ electrode without electron loss. Moreover, the recombination was also much slower in the TiO₂ (bottom)/B_x–TiO₂ (top)-based DSSCs than in the double-layered pure TiO₂ DSSC.     

Thickness effect of RF sputtered TiO2 passivating layer on the performance of dye-sensitized solar cells

We report on the characteristics of a TiO₂ passivating layer grown by radio frequency (RF) magnetron sputtering on F-doped SnO₂ (FTO) electrodes as a function of its thickness. The optical transparency, surface roughness and passivation properties of the TiO₂ layer passivating the FTO electrode depend on the thickness of the TiO₂ passivating layer. In addition, it was found that the power conversion efficiency of the dye-sensitized solar cells (DSSCs) is critically dependent on the thickness of RF sputtered TiO₂ layer inserted between FTO electrode and nanoporous TiO₂ layer. The DSSC fabricated on 50 nm thick TiO₂ passivating FTO electrode showed the maximum power conversion efficiency of 4.42% due to effective prevention of the electron transfer to electrolyte. This indicates that the thickness optimization of the TiO₂ passivating layer is one of the important parameter to obtain high performance DSSCs.     

Synthesis and characterisation of Cu - Doped TiO2 nanoparticles for DSSC and photocatalytic applications

In the present work, copper-doped TiO₂ nanoparticles were synthesized via sol-gel technique with different molar concentration of copper precursor (0.025 M-CT-1, 0.05 M-CT-2, 0.1 M-CT-3 and 0.2 M-CT-4). The effect of copper doping on the structural, morphological, compositional, optical and electrical properties of TiO₂ was systematically analyzed for its better suitability as photoanode in Dye-Sensitized Solar Cells (DSSC) and photocatalyst in dye degradation. From structural analysis, all the synthesized samples show anatase phase with a tetragonal crystal system. The broadening and shift in the peaks of the synthesized samples show the successful incorporation of Cu ions into TiO₂ lattices. All the synthesized samples exhibit spherical shape morphology with slight agglomeration. EDS analysis exhibit the purity of the synthesized nanoparticles with the presence of only Ti, O, and Cu. UV-DRS analysis reveals the decrease in reflectance of the TiO₂ with increasing the Cu concentration. The bandgap values of the Cu–TiO₂ decreased from 2.66 to 2.40 eV with the increase of copper concentration. From PL analysis, the peak observed at 380.20, 469.56 and 535.24 nm corresponds to the band-band PL emission, free excitons, and oxygen vacancies, respectively. Further, we have fabricated DSSC using Cu-doped TiO₂ as a photoanode without treatment of any scattering layer and we have obtained the maximum efficiency of 3.90% for 0.1 M Cu–TiO₂ (CT-3). Similarly, the maximum degradation efficiency of 97.12% was obtained against rhodamine-B dye with the highest regression coefficient (R² = 0.9957) and lesser half-life degradation time (t_1/2 = 47.1428 min) for CT-3. This higher efficiency was not reported elsewhere using Cu-dopant concentrations. From these observations, it was concluded that 0.1 M concentration of Cu was the optimum dopant concentration with TiO₂ which was suitable for DSSC and photocatalytic applications.     

TiO2/ZnO/TiO2 sandwich multi‐layer films as a hole‐blocking layer for efficient perovskite solar cells

A continuous and compact hole‐blocking layer is crucial to prevent photocurrent recombination at the photoanode/electrode interface of high‐performance mesostructure perovskite‐based solar cells. Novel TiO₂/ZnO/TiO₂ sandwich multi‐layer compact film prepared as hole‐blocking layer for perovskite solar cell. Herein, TiO₂, ZnO, and TiO₂ layers were successfully deposited by spin‐coating onto FTO glass substrate in sequence. The fill factor and power conversion efficiency of the perovskite solar cell are remarkably improved by the employment of a TiO₂/ZnO/TiO₂ sandwich compact layer. Perovskite solar cell based on TiO₂/ZnO/TiO₂ sandwich film has been observed to exhibit maximum incident‐photon‐to‐current conversion efficiency in the visible region (400–780 nm) and reach a power conversion efficiency of 12.8% under AM1.5G illumination. Copyright © 2016 John Wiley & Sons, Ltd.     

CTAB facilitated spherical rutile TiO2 particles and their advantage in a dye-sensitized solar cell

Spherical rutile TiO₂ particles (14–20 nm) and their corresponding well-defined round clusters (500–600 nm) were obtained by using a cationic surfactant cetyltrimethylammonium bromide (CTAB). The surfactant was employed in two stages, i.e., in the hydrolysis of TiCl₄ and then in the precipitation of the corresponding Ti(IV) polymers at approximately 46 °C. On the other hand, without CTAB in the hydrolyzing solution, irregular clusters consisting of typical ellipsoidal TiO₂ particles were produced. The advantage of such spherical rutile TiO₂ particles and clusters was examined in terms of photovoltaic characteristics of a dye-sensitized solar cell (DSSC). Significantly higher overall solar energy conversion efficiency was obtained for a DSSC using the film of these spherical rutile TiO₂ particles, compared with that of a cell using a TiO₂ film of ellipsoidal particles. A mechanism for the formation of these spherical rutile particles and clusters is proposed.     

On the photophysical and electrochemical studies of dye-sensitized solar cells with the new dye CYC-B1

In this study, the photoelectrochemical characteristics of a ruthenium photosensitizer with an alkyl bithiophene group, designated as CYC-B1, are studied. The effect of mesoporous TiO₂ film thickness on the photovoltaic performance of CYC-B1 and N3 dye-sensitized solar cells was investigated. The performance of the dye-sensitized nanocrystalline TiO₂ solar cells (DSSC) fabricated using CYC-B1 dye-anchored TiO₂ photoelectrode showed a convincing enhancement in cell efficiency when the TiO₂ film thickness was increased from 3 μm (eff.=5.41%) to 6 μm (eff.=7.19%). The efficiency of the CYC-B1-sensitized DSSC was maximum at 6 μm of the TiO₂ film thickness, reached its limiting value and remained constant up to 53 μm, although a similar trend was also observed for N3 dye-sensitized DSSC, however, the maximum efficiency achieved was only at 27 μm thickness (eff.=6.75%). As expected, the photocurrent density generated in the DSSC modified by CYC-B1 dye is larger than that from N3 dye. The effect of guanidinium thiocyanate (GuSCN) (additive) addition to the electrolyte on the photovoltaic performance of DSSCs based on CYC-B1 was also investigated. Furthermore, the electrochemical impedance spectroscopy (EIS) technique and photo-transient laser method have been employed to analyze the charge transfer resistances (R_ct) and the lifetime of the injected electrons on the TiO₂ containing different thicknesses.     

The effects of hydrothermal temperature and thickness of TiO2 film on the performance of a dye-sensitized solar cell

The effects of hydrothermal temperature on the preparation of TiO₂ colloids, and their film thickness on fluorine-doped tin oxide (FTO) glass, toward the performance of a dye-sensitized solar cell (DSSC) were investigated. Pore diameter and surface area of the TiO₂ are of paramount importance in determining the cell efficiency. With the increase of hydrothermal temperature, the pore diameter increases linearly; however, the surface area shows the reverse effect. It is found that the DSSC assembled with the TiO₂ films prepared under the hydrothermal temperature of 240 °C, and the film thickness larger than 10 μm gives optimal performance. The effect of film thickness of TiO₂ on the performance of the DSSC can be explained by the relative size of reactive species diffusing into the thin film and the lifetime of injected electrons. Electrochemical impedance spectroscopy (EIS) was also used to analyze the resistance of the cell, developed as a result of the change in the thickness of the TiO₂ thin film. The at-rest stability for over 200 days was monitored and the results show that the solar energy conversion efficiency was found to decrease from 5.0% of initial value to 3.0% at the end.     

Improved performance of dye-sensitized solar cells with TiO2/alumina core-shell formation using atomic layer deposition

Alumina (Al₂O₃) shell formation on TiO₂ core nanoparticles by atomic layer deposition (ALD) is studied to suppress the recombination of charge carriers generated in a dye-sensitized solar cell (DSSC). It is relatively easy to control the shell thickness using the ALD method by controlling the number of cycles. An optimum thickness can be identified, which allows tunneling of the forward current while suppressing recombination. High-resolution TEM measurements show that a uniform Al₂O₃ shell is formed around the TiO₂ core particles and elemental mapping of the porous TiO₂ layer reveals that the Al₂O₃ distribution is uniform throughout the layer. The amount of dye absorption is increased with increase in the shell thickness but electrochemical impedance spectroscopic (EIS) measurement shows a drastic increase in the resistance. With an optimum Al₂O₃ thickness of 2 nm deposited by ALD, a 35% improvement in the cell efficiency (from 6.2 to 8.4%) is achieved.     

Low-temperature oxygen plasma treatment of TiO2 film for enhanced performance of dye-sensitized solar cells

The effects of low-temperature O₂ plasma treatment of a TiO₂ film are studied with the objective of improving the performance of dye-sensitized solar cells (DSSCs). X-ray photoelectron spectra (XPS) reveal that the ratio of titanium dioxide to titanium sub-oxides is increased in the O₂ plasma-treated TiO₂ film, compared with that of the untreated TiO₂ film. This increase suggests that the oxygen vacancies in the film are effectively reduced. The near-edge X-ray absorption fine structure (NEXAFS) spectra results agree with the XPS result. It is proposed that there is a correlation between the shifts of the peaks in the NEXAFS spectra and the adsorption of N719 dye on the TiO₂ particles. A DSSC having an O₂ plasma-treated, 4 μm thick TiO₂ film electrode renders a short-circuit photocurrent of 7.59 mA cm⁻², compared with 6.53 mA cm⁻² for a reference cell with an untreated TiO₂ electrode of the same thickness. As a result of these changes, the solar-to-electricity conversion efficiency of the O₂ plasma-treated cell is found to be 4.0% as compared with 3.5% for the untreated cell. This improvement in the performance is rationalized on the basis of increased N719 dye adsorption on to the TiO₂, due to the reduction in the number of oxygen vacancies caused by the oxygen plasma treatment.     

Surface selective passivation and FexNi1-xOOH co-modified Fe2O3 photoanode toward high-performance water oxidation

Improving the water-splitting performance of hematite (α-Fe₂O₃) is still hindered due to its severe charge recombination and poor water oxidation kinetics. Herein, borate-treated Ti–Fe₂O₃ combined with a Fe_xNi_1-xOOH cocatalyst (Fe_xNi_1-xOOH/B/Ti–Fe₂O₃) greatly improved the performance of Ti–Fe₂O₃, and reached a notable photocurrent density of 3.39 mA/cm² at 1.23 V vs. RHE. Transient surface photovoltage spectroscopy (TPV) directly reveals that [B(OH)₄]^? as a Lewis base can selectively passivate acceptor surface states on Ti–Fe₂O₃ photoanode surface, efficiently enhancing the charge separation efficiency. Moreover, the Fe_xNi_1-xOOH thin layer is devoted to further facilitate holes injection into the electrolyte, accelerating the water oxidation kinetics of Ti–Fe₂O₃ photoanode. The synergetic integration of acceptor surface states passivation and Fe_xNi_1-xOOH cocatalyst provides a novel strategy for the construction of efficient photoanodes by surface engineering.     

Surface engineering of CeO2–TiO2 composite electrode for enhanced electron transport characteristics and alkaline hydrogen evolution reaction

Herein, we report the fine tuning of electrocatalytic characteristics of CeO₂–TiO₂ composite by surface engineering to reduce overpotential and to improve exchange current density for enhanced alkaline hydrogen evolution reaction (HER). The enhanced electrocatalytic activity of the surface engineered CeO₂–TiO₂ composite through Ni and P decoration is attributed to the improved electron transport ability. The surface roughness characteristics and surface composition of electroactive species are tuned to generate high electronic conductivity on the surface engineered composite electrode surface. The developed hard electrode with leptokurtic surface (S_ku > 3) exhibited a high average roughness value (Sa) of 3 μm due to incorporation of the mesoporous catalyst material into it. Tuning of a compact and continuous electrode surface with critical composition of elements Ni (52 at.%), P (20 at.%), Ce (9 at.%) and Ti (8 at.%) furnishes the high conductivity (contact potential difference = 0.83 V) to the electrode. The developed electrode with surface engineered CeO₂–TiO₂ catalyst exhibited a low overpotential of −111 mV (at a high current density of 250 mA cm⁻²) and high exchange current density (1.6 × 10⁻¹ mA cm⁻²) with low charge transfer resistance (615 Ω cm²). High electrocatalytic activity and stability of the surface engineered CeO₂–TiO₂ catalyst electrode during alkaline (32 w/v.% NaOH) HER ensure its promising performance and applicability for long term HER.     

Core-shell hetero-phase reduced Ti–Ni–O nanotubes photoanode with enhanced optical absorption and charge transport for boosted photoelectrochemical water splitting

Bulk-phase doping and surface oxygen-defective engineering of TiO₂-based nanostructures are identified as effective routes for enhanced photoelectrochemical (PEC) water splitting. Here, we reported a reduced Ti–Ni–O nanotubes photoanode with anatase-rutile crystalline-core and oxygen vavancies amorphous-shell for boosted PEC water splitting. The core-shell hetero-phase reduced Ti–Ni–O nanotubes were fabricated through phase-structure modulation by a thermal treatment of anodized Ti–Ni–O nanotubes on Ti–Ni alloy and with one-step electrochemical reduction. Microstructure, optical and PEC measurement results confirmed effective bulk-phase Ni-doping and surface oxygen vacancies self-doping into the reduced mixed-phase Ti–Ni–O nanotubes, which enabled high capability of optical-absorption and simultaneously favored charge separation-transfer for remarkably improved the PEC water splitting. A higher photocurrent density of 1.66 mA/cm² at 0 V vs. Ag/AgCl and solar-to-hydrogen efficiency of 0.79% were achieved for the reduced Ti–Ni–O system, which was 5.35 and 5.27 times that of undoped TiO₂, respectively. This work may shed an insight view on fabricating high-performance Ti-based nano-photoanodes with enhanced light harvesting and carrier kinetics for efficient PEC water splitting, through synergistic strategy of bulk-phase elements doping and surface oxygen vacancies self-doping.     

Organic photosensitizers containing fused indole-imidazole ancillary acceptor with triphenylamine donor moieties for efficient dye-sensitized solar cells

Controlling the morphology of sensitizer on a TiO₂ nanocrystalline surface is beneficial to facilitating electron injection and suppressing charge recombination. Given that the N,N-dimethylaniline-substituted imidazole-fused-indole on the middle segment for preventing π aggregation can deteriorate its intrinsic photostability, we incorporate a promising building block of fused-indole-imidazole [(1,4-dihydroimidazo[4,5-b]indole) DHII)] ring as the additional acceptor to construct a novel TD₂, TD₃ and YD₃ with D–(A)π-D, D–(DA₂)π-D, D–π-D(A)-π-D architecture, which exhibits several characteristics: (i) possible chelation of imidazole ring (through N) to the titanium ions on the TiO₂ surface which can assist in increasing the electron injection into the conduction band of photoanode, (ii) showing a moderate electron-withdrawing capability for an ideal push-pull balance in both promising photocurrent and photovoltage; (iii) endowing an ideal morphology control with strong capability of restraining the intermolecular aggregation and facilitating the formation of a compact sensitizer layer via N,N-dimethylaniline groups grafted onto the fused-indole-imidazole unit. The co-adsorbent-free dye-sensitized solar cell (DSSC) based on dye TD₃ exhibits very promising conversion efficiency as high as 6.04 ± 0.01%, with a short-circuit current density (J_sc) of 13.57 mA cm^?2, an open-circuit voltage (V_oc) of 0.80 V, and a fill factor (FF) of 0.774 under AM 1.5 illumination (100 mW cm^?2). TD₃-based device showed better performance because of the two anchoring groups, which play a significant role for better adsorption on the TiO₂ surface along with the enhanced kinetics of photoexcited electron injection.     

Algal buffer layers for enhancing the efficiency of anthocyanins extracted from rose petals for natural dye‐sensitized solar cell (DSSC)

Natural dye‐sensitized solar cells (DSSCs) are becoming promising candidates for replacing synthetic dyes. Anthocyanins, a flavonoid pigment which is responsible for the coloration in fruits and flowers, have shown productive results in employing them as natural dye for DSSC. But unfortunately, they exhibit low efficiency compared with synthetic dyes. Probing the reasons for the low efficiency of anthocyanin paves way for finding solution to increase the efficiency. This paper lists the important factors that are responsible for anthocyanin instability in DSSC. As a remedial measure, this paper introduces two buffer layer made of algal byproducts—sodium alginate and Spirulina. Rutile phase TiO₂ nanorods prepared by hydrothermal method were used as photoelectrode and are subsequently characterized by X ray diffraction, transmission electron microscopy, and optical studies. The use of sodium alginate above the photoelectrode has proved to improve the dye concentration in the film by introducing more hydroxyl groups on the surface of TiO₂. Anthocyanins extracted from rose petals using citric acid as solvent were used as dye for DSSC. Prior to the sensitization process with anthocyanin dye, the TiO₂ film (with sodium alginate) was sensitized with Spirulina. The chlorophylls, xanthophylls, phycocyanins, and amino acids present in Spirulina assist the anthocyanins to bond with TiO₂ efficiently. This helps in enhancing the efficiency of anthocyanins of rose dye from 0.99% to 1.47%.     

Photoelectrochemical water splitting by engineered multilayer TiO2/GQDs photoanode with cascade charge transfer structure

Herein, for the first time, an efficient photoanode engineered with the cascade structure of FTO|c-TiO₂|few graphene layers|TiO₂/GQDs|Ni(OH)₂ assembly (Ni(OH)₂ photoanode) is designed. This photoanode exhibited much lower electron–hole recombination, fast charge transport, higher visible light harvesting, and excellent performance with respect to FTO|c-TiO₂|TiO₂ assembly (TiO₂ photoanode) in the photoelectrocatalytic oxygen evolution process. The photocurrent density of Ni(OH)₂ photoanode is 7 times (0.35 mA cm⁻² at 1.23 V vs. RHE) greater than that of TiO₂ photoanode (0.045 mA cm⁻² at 1.23 V vs. RHE). The compact TiO₂ (c-TiO₂) layer in Ni(OH)₂ photoanode plays a role of an effective hole-blocking layer. Few-layer graphene layer could speed up the transport of the photogenerated electrons from the conduction band of the TiO₂/GQDs to FTO. Ni(OH)₂ layer could transfer rapidly holes into electrolyte solution.     

High-efficiency photoelectrochemical water splitting with heterojunction photoanode of In2O3-x nanorods/black Ti–Si–O nanotubes

Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO₂-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In₂O₃ (In₂O_3-x) nanorods/black Si-doped TiO₂ (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In₂O_3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO₂. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti³⁺/oxygen vacancy as well as In₂O_3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO₂-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.     

Influences of different TiO2 morphologies and solvents on the photovoltaic performance of dye-sensitized solar cells

The effects of TiO₂ photoelectrode's surface morphology and different solvents on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were studied. By successive coating of TiO₂ suspension, composed of low and high molecular weight poly(ethylene)glycol (PEG) as a binder, double layered TiO₂ photoelectrodes with four different structures were obtained. Among the DSSCs with different TiO₂ electrodes, DSSC with P2P1 electrode (P2 and P1 correspond to PEG molecular weights of 20,000 and 200,000, respectively) showed higher performance under identical film thickness at a constant irradiation of 100 mW cm⁻², which may be correlated with large pore size and high surface area of the corresponding TiO₂ electrode. This was confirmed by electrochemical impedance spectroscopy (EIS) analysis of the DSSC and the transient photovoltage measurement of electrons in the TiO₂ electrode. Among the different solvents investigated here, the DSSC containing acetonitrile showed high conversion efficiency and the order of performance of the DSSCs with different solvents were AN > MPN > PC > GBL > DMA > DMF > DMSO. Better correlation was observed between the donor number of solvents and photoelectrochemical parameters of the DSSCs containing different solvents rather than the measured viscosity and dielectric constant of solvents. The reasons for the low performance of the DSSCs containing DMA, DMSO and DMF, respectively, were due to the negative shift of TiO₂ conduction band and the desorption of dye molecules from the TiO₂ photoelectrode by those solvents.