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%.     

Novel dye based photoelectrode for improvement of solar cell conversion efficiency

We have explored the application of natural dyes extracted from beetroot in Dye sensitized solar cell (DSSC). The main pigment is betacyanin which was obtained by separation and purification from the extract. The photo electrochemical performance of the DSSC based on these dyes showed that the photo voltage and photocurrent 435 mV, 9.86 mA, respectively. The overall conversion efficiency of nano WO₃ coated TiO₂ dye-sensitized solar cells exhibits a higher conversion efficiency of 2.2%. The photo electrochemical performance of beetroot extract demonstrate that betacyanin dye was the most effectual component of the sensitizer for DSSC because of the simple preparation technique, widely available and low cheap cost.     

Soft‐template synthesis of high surface area mesoporous titanium dioxide for dye‐sensitized solar cells

In the present work, 10 to 14 nm titania nanoparticles with high‐packing density are synthesized by the soft‐template method using a range of cationic surfactants including cetyl trimethylammonium bromide (CTAB), Sodium dodecyl sulfate (SDS), and dodecyl trimethylammonium bromide (DTAB). The synthesized nanoparticles are used as a photoanode material in dye solar cells. Density functional theory (DFT) simulations reproduce our experimental results of charge transfer and strong interaction between the TiO₂ and N719. N719‐TiO₂ complex establishes strong electrostatic bonding through H of the dye with the O of TiO₂ surface. Solar cell efficiency of 6.08% with 12.63 mA/cm², 793 mV, and 48.5% for short circuit current density, open circuit voltage, and fill factor, respectively, are obtained under 1 sun illumination for the dye‐sensitized solar cell (DSSC) using a film of mesoporous TiO₂ synthesized from the SDS surfactant. On the other hand, the 21 nm commercial TiO₂ powder (P25) device results in 4.60% efficiency under similar conditions. Electrochemical impedance spectroscopic studies show that the SDS device has lesser charge transport resistance than the other devices because of its higher surface area, packing density, and dye loading capacity. Our results show that employing high packing density‐based TiO₂ nanoparticles represents a commercially viable approach for highly beneficial photoanode development for future DSSC applications.     

Dye-sensitized solar cell using natural dyes extracted from rosella and blue pea flowers

Dye-sensitized solar cells (DSSCs) were fabricated using natural dyes extracted from rosella, blue pea and a mixture of the extracts. The light absorption spectrum of the mixed extract contained peaks corresponding to the contributions from both rosella and blue pea extracts. However, the mixed extract adsorbed on TiO₂ does not show synergistic light absorption and photosensitization compared to the individual extracts. Instead, the cell sensitized by the rosella extract alone showed the best sensitization, which was in agreement with the broadest spectrum of the extract adsorbed on TiO₂ film. In case that the dyes were extracted at , using water as extracting solvent, the energy conversion efficiency (η) of the cells consisting of rosella extract alone, blue pea extract alone and mixed extract was 0.37%, 0.05% and 0.15%, respectively. The sensitization performance related to interaction between the dye and TiO₂ surface is discussed. The explanations are supported by the light absorption of the extract solution compared to extracts adsorbed on TiO₂ and also dye structures. The effects of changing extracting temperature, extracting solvent and pH of the extract solution are also reported. The efficiency of rosella extract sensitized DSSC was improved from 0.37% to 0.70% when the aqueous dye was extracted at instead of and pH of the dye was adjusted from 3.2 to 1.0. Moreover, DSSC stability was also improved by the changes in conditions. However, the efficiency of a DSSC using ethanol as extracting solvent was found to be diminished after being exposed to the simulated sunlight for a short period.     

Effect of using betalain,anthocyanin and chlorophyll dyes together as a sensitizer on enhancing the efficiency of dye-sensitized solar cell

The paper explored the mechanism of working of dye sensitizers for the improvement of efficiency of environmentally benign dye-sensitized solar cells (DSSC). The identified natural dyes namely anthocyanin (A), betalain (B) and chlorophyll (C) were extracted from Roselle (Hibiscus sabdariffa L.), spinach (Spinacia oleracea) and beetroot (Beta vulgaris) respectively. Light absorption performance of dyes was recorded by ultraviolet-visible (UV-vis) spectroscopic analysis followed by direct and indirect band gap calculation. The effect of functional groups present in the dyes studied by Fourier transform infrared spectroscopy (FTIR) and binding of the dyes on TiO₂ through surface morphology of sheets was identified employing field emission scanning electron microscopy (FESEM). Photovoltage characteristics (I-V) and induced photon to current efficiency (IPCE) measurements were also noted followed by the stability studies. The N3 (synthetic dye chosen for the reference) dye-based cell showed the highest efficiency of 6.19% out of all of 11 cells fabricated using different sensitizers. The DSSC fabricated using the novel mixed dye (ABC) mixture gave the highest efficiency of 3.73%, however it showed similar drop (almost 22%) in efficiency as that with of N3 dye in stability studies. The mechanism for the increase in the overall power conversion efficiency of DSSC was also suggested.     

3D graphene from CO2 and K as an excellent counter electrode for dye‐sensitized solar cells

3D graphene, which was synthesized directly from CO₂ via its exothermic reaction with liquid K, exhibited excellent performance as a counter electrode for a dye‐sensitized solar cell (DSSC). The DSSC has achieved a high power conversion efficiency of 8.25%, which is 10 times larger than that (0.74%) of a DSSC with a counter electrode of the regular graphene synthesized via chemical exfoliation of graphite. The efficiency is even higher than that (7.73%) of a dye‐sensitized solar cell with an expensive standard Pt counter electrode. This work provides a novel approach to utilize a greenhouse gas for DSSCs.     

N‐doped titania powders prepared by different nitrogen sources and their application in quasi‐solid state dye‐sensitized solar cells

Nitrogen‐doped TiO₂ nanocrystalline particles are synthesized by a microwave‐assisted hydrothermal growth method using different amines (Dipropylamine, Diethanolamine and Ammonium hydroxide) as nitrogen sources. Characterization of the nanoparticles was performed with X‐ray diffraction, UV–vis diffuse reflectance spectroscopy, Field Emission Scanning Electron Microscopy and X‐ray Photoelectron Spectroscopy. The prepared N‐doped TiO₂ nanoparticles exhibit pure anatase phase with average diameter of 9 nm and reduced optical energy gap compared to undoped TiO₂. Immobilization of N‐doped and pure TiO₂ nanoparticles on SnO₂:F conductive glass substrates was successfully performed by using doctor‐blade technique and paste of the aforementioned nanoparticles. A series of N‐doped TiO₂ photoelectrodes with varying N dopant source and concentrations were fabricated for quasi‐solid state dye‐sensitized solar cells. The N‐doped solar cells achieve an overall conversion efficiency ranging from 4.0 to 5.7% while undoped TiO₂ showed 3.6%. The basic difference to the electrical performance of the cells is focused to the enhancement in the current density of N‐doped TiO₂‐based cells which was from 11% to 58% compared with undoped TiO₂ cells. Current densities were directly proportional with nitrogen doping level in TiO₂ lattice which differs depending on the amine source nature such as basicity differences, hydrogen bonding abilities and steric inherences. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

St. Lucie cherry,yellow jasmine,and madder berries as novel natural sensitizers for dye‐sensitized solar cells

Natural dyes extracted from fruits, vegetables, flowers, and leaves are considered as promising alternative sensitizers to replace synthetic dyes for dye‐sensitized solar cells (DSSCs). Generally, solar activity of natural dyes stem from anthocyanin pigment. Carbonyl, carboxyl, and hydroxyl groups present in the anthocyanin molecule improve the adsorption ability of dye on TiO₂ and therefore facilitate charge transfer. Here, for the first time, novel natural dyes extracted from St. Lucie cherry, yellow jasmine, and madder berries are reported to act as sensitizer in DSSCs. These novel natural dye extracts are prepared by dissolving related fruits in ethanol. The ingredient of the dyes is identified by FT‐IR spectroscopy. Accordingly, FT‐IR spectrum reveals that novel natural dye extracts exhibit all the characteristic peaks of anthocyanin pigment. Specifically, St. Lucie cherry consists of more distinct carbonyl group than other sources. Also, photoanodes composed of three TiO₂ layers are prepared by using a spin‐coating method. Then, they are immersed into natural dyes and analyzed by conducting UV‐Vis spectroscopy. Compared with bare TiO₂, natural dye–loaded photoanodes demonstrate far higher absorption ability in the visible region. After fabrication of devices with different novel natural dye sensitizers, current‐voltage characteristics and electrochemical impedance spectroscopy measurements are performed. The best power conversion efficiency (PCE) of 0.19% is obtained by sensitization of St. Lucie cherry with an open‐circuit voltage (V_oc) of 0.56 V, short‐circuit current density (J_sc) of 181 μA cm^?2, and fill factor (FF) of 0.55. Furthermore, St. Lucie cherry–sensitized devices show the lowest charge transfer and highest recombination resistances. This result can be attributed to the obvious carbonyl group exhibited by St. Lucie cherry.     

Enhanced DSSC performance with high surface area thin anatase TiO2 nanoleaves

Thin anatase TiO₂ nanoleaves (NLs) with high surface area (∼93 m²/g) are synthesized by hydrothermal route and dye-sensitized solar cells (DSSC) made using such NLs are compared with those made with hydro-thermally synthesized TiO₂ nanoparticles and the Degussa P25 powder. The NLs-based DSSCs show increment of 16% and 24% in the total conversion efficiency over the cells made with NPs and P25 respectively. Interestingly, the highest increment in the conversion efficiency (∼35%) is achieved for cells made using a 50:50 (wt/wt) mixture of NLs and NPs. In this case the dye loading is found to be >50% higher than the case of NP films. Moreover the DC resistance of diffusion of in electrolyte (as revealed by the electrochemical impedance spectroscopy) is substantially lower than the NP film case, other cell parameters being nominally comparable.     

Aqueous dye-sensitized solar cell based on new ruthenium diphenyl carbazide complexes

The major challenge of the operation of every solar cell based on dye including water splitting solar cell (WSSC) and dye sensitized solar cell (DSSC) is the using organic solvent medium which causes to decompose the solar cell structure, resulting environmental impact. Here, we synthesized and characterized two new ruthenium complexes with nitrogen and oxygen donor ligands for DSSC application which show good stability on TiO₂ surface in water solvent. Interestingly, the DSSC based on [Ru(dcbpy)₂(DPC)]Cl, where dcbpy = 4,4-dicarboxilic acid 2,2-bipyridin and DPC = diphenylcarbazide, was shown better efficiency in water than methanol dye loading as well as N3 as a benchmark sensitizer in the same condition. The DPC-based exhibited open circuit voltage (V_oc) of 0.63 V, short-circuit current density (J_sc) of 2.5 mA/cm² and fill factor (FF) of 70%, resulting an overall power efficiency of 1.12%. The incident-photon-to-current conversion efficiency (IPCE) value is also reached to 45% for [Ru(dcbpy)₂(DPC)]Cl in the same condition It is proposed that the ruthenium complex containing nitrogen and oxygen donor ligands is more stability on TiO₂ and prevent the decomposition of TiO₂ porous under water solvent condition.     

Hydrothermally synthesized TiO2 nanopowders and their use as photoanodes in dye‐sensitized solar cells

TiO₂ nanopowders are synthesized using a hydrothermal process under various conditions. Effects of several hydrothermal conditions are investigated such that the TiO₂ nanopowders having optimized size, surface area, crystallinity, and yield are used for the fabrication of photoanodes. The obtained TiO₂ photoanodes are subjected to oxygen plasma treatments for various times. As‐synthesized and plasma‐treated photoanodes are then assembled into dye‐sensitized solar cells. The plasma‐treated photoanodes exhibit different concentrations of surface C–OH and oxygen vacancies, depending on the plasma treatment times. This leads to dye‐sensitized solar cells having different conversion efficiencies. The use of plasma treatment can enhance the cell conversion efficiency by more than 24%. The effects of the photoanode surface condition on the performance of photoanode are discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhancement in the photostability of natural dyes for dye‐sensitized solar cell (DSSC) applications: a review

The advancements in the generation of solar cells have created a landmark to design a cost‐effective, less weight, biocompatible, and environmental‐friendly solar cell. Dye‐sensitized solar cells (DSSCs) have become a topic of significant research in the recent years because of their imperative role in the zone of harvesting energy from the renewable source, and it appears to be a promising candidate for the triumph because of its low cost and ease of preparation. The use of synthetic dyes as a sensitizer for DSSC provides better efficiency and high durability. Unfortunately, they suffer from several margins such as higher cost and usage of toxic materials. These downsides have opened up for alternative sensitizer such as biocompatible natural dyes. Natural dyes contain plant pigments such as carotenoid, flavonoid, betalains, and chlorophyll that act as sensitizers (dye) for DSSC. But, the efficiency of natural dyes is not up to the mark mainly due to photoinstability of natural dye in the presence of sunlight that leads to photodegradation. The stability issues are mainly due to interaction of natural dyes with photoelectrode. The photoelectrodes in DSSC are semiconductor materials with superior characteristic of photocatalytic activity (PCA). The PCA of titanium dioxide (TiO₂) generates high energetic free electrons on the surface of film that produce free radical ions in contact with moisture. These free radical ions readily degrade the organic matter present nearby (natural dye in DSSC). Thus, the PCA of photoelectrode is responsible for the photodegradation of dyes causing photoinstability. The main objective of this review is to study the photoinstability of natural dyes in DSSC. In this regard, the DSSC is concentrated into sections, and the stability issues due to PCA of photoelectrode are studied individually in the view of considering the DSSC operating with iodide‐based electrolytes and platinum as counter electrode only. Various algae groups are featured as a study tool to overview the dye interaction with photoelectrode. It highlights the application of Z‐scheme of photosynthesis to DSSC to have a broader perception on the working of DSSC and also shows some of the ways for improving the stability of dyes by suppressing or reducing the PCA of photoelectrode. Copyright © 2017 John Wiley & Sons, Ltd.     

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.     

天然染料敏化太阳能电池性能模拟研究

基于电子传输的扩散理论建立了染料敏化太阳能电池（DSSC）的连续性方程,并在扩散方程的基础上,将单一天然染料及混合天然染料的吸收光谱参数引入连续性方程中,对模拟得到的天然染料的伏安特性曲线进行分析与评价,得到了高效率的天然染料及最优天然染料组合。本研究对天然染料敏化太阳能电池的应用与技术发展具有一定的指导意义。     

Efficient sensitization of nanocrystalline TiO2 films with cyanine and merocyanine organic dyes

Various kinds of cyanine and merocyanine organic dyes having short anchoring groups as sensitizers on nanocrystalline TiO₂ electrodes were investigated to promote the short-circuit photocurrent (J_sc) and the solar light-to-power conversion efficiency (η_sun). The J_sc and η_sun improved when the three different three dyes (yellow and red cyanine dyes, and blue squarylium cyanine dye) were adsorbed simultaneously on a TiO₂ electrode, as compared with the J_sc and η_sun of the TiO₂ electrodes adsorbed by each single dye. The maximum η_sun was 3.1% (AM-1.5, 100 mW/cm²). The J_sc and η_sun were influenced by the solvents for the dye adsorption on the TiO₂ electrode, and the efficiencies were improved by the addition of some cholic acids into the dye solution for adsorption. The electron transfer and/or the energy transfer from the red cyanine dye to the blue cyanine dye was observed on a SiO₂ film using emission spectroscopy, suggesting a strong interaction between two dyes. The J-like aggregates of the blue cyanine dyes hardly showed sensitization efficiency.     

A new method to evaluate the feasibility of a dye in DSSC application

Search for better photo sensitizers has always been a challenge in the field of dye sensitized solar cell (DSSC). This paper suggests a new method to identify a good dye for DSSC through the evaluation of energy levels of dye–TiO₂ complex. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the complex are evaluated using cyclic voltammetry (CV) and spectroscopic technique. These energy levels have been used to predict the performance of the solar cell even without fabricating a cell. The authenticity of this method is also revalidated through the correlation of efficiency of practical cell. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis, photophysics of two new perylene bisimides and their photovoltaic performances in quasi solid state dye sensitized solar cells

Two new symmetrical compounds A and P based on perylene-anthracene and perylene-pyrene, respectively, were synthesized and characterized by FT-IR, ¹H NMR, TGA and TMA. These compounds contained tert-butyl groups which enhanced their solubility, decomposed above 400 °C and gave char yields of 46–65% at 800 °C in N₂. Compound A showed significantly higher glass transition temperature (124 °C) than P (75 °C). Their absorption spectra were broad with longer wavelength absorption at 467–525 nm and optical band gap of 2.05 eV. The solutions of the compounds emitted green-yellow light with maximum at 555 nm, while their films were not photoluminescent. The compound A shows better photovoltaic response than compound P. Quasi solid state dye sensitized solar cells (DSSCs) have been fabricated employing compound A as sensitizer and polymer sol gel as electrolyte and characterized through the current–voltage characteristics in dark as well as under illumination and electrochemical impedance spectra. We found that the Al₂O₃ modification of TiO₂ layer significantly improves the dye absorption resulting in enhancement of power conversion efficiency (PCE) (from 1.15 to 2.13%) which is attributed to the increase in electron lifetime and reduction in back transfer of electrons. Finally, the TiO₂ has been incorporated into the polymer electrolyte gel to improve the power conversion efficiency (3.42%) of the quasi solid state DSSC. The faster electron diffusion in the device, the high ionic conductivity and the low activation energy of the polymer electrolyte are also responsible for enhanced PCE, when TiO₂ nano-particles are incorporated in the polymer electrolyte.     

Deprotonated curcumin as a simple and quick available natural dye for dye sensitized solar cells

In the present study, deprotonation of curcumin dye using potassium carbonate was performed successfully, which produced fairly stable deprotonated dye with a large bathochromic shift in the visible light absorption spectrum. The light-harvesting efficiency of this deprotonated dye was investigated in TiO₂-based dye sensitized solar cells, which exhibited an energy conversion efficiency of 0.91%, and this value is 8.3 times higher than that of the dye sensitized solar cells with curcumin photosensitizer without deprotonation.     

Hydrogen treated TiO2 nanoparticles onto FTO glass as photoanode for dye-sensitized solar cells with remarkably enhanced performance

Hydrogen treatment is a facile and efficient approach for the enhancement in the functioning of TiO₂ nanoparticles for dye-sensitized solar cells (DSSC). In this work, TiO₂ nanoparticles have been synthesized in the hydrogen environment followed by the deposition onto FTO glass substrates with various film thickness as photoanodes for DSSC. The synthesized hydrogen treated TiO₂ nanoparticles based photoanodes have showed significantly improved photocurrent in the resulting fabricated devices. SEM and TEM analyses have confirmed the particle size and morphology of TiO₂ nanoparticles at various magnifications. The crystalline structure and phase identification were studied by XRD analysis and Raman spectroscopic measurements. The UV–Vis spectroscopy analysis was carried out to find the response of samples for ultraviolet and visible light. The current-voltage measurements have confirmed the improvement of photocurrent that is principally due to improved photo-activity of hydrogen treated TiO₂ nanoparticles. Moreover, hydrogen treated TiO₂ nanoparticles-based photoanode with the film thickness of 11.65 μm has remarkably enhanced power conversion efficiency of 6.05% in DSSCs. The ability of highly photoactive hydrogen treated TiO₂ nanoparticles will provide the new openings in different fields that include photo-electrochemical water splitting and in many other applications.