Synthesis of TiO2 nanoparticles at low hydrothermal temperature and its performance for DSSC sensitized using natural dye extracted from Melastoma malabathricum L. seeds

Efficiency of a dye‐sensitized solar cell (DSSC) device depends on its semiconductor layer and the sensitizing dye to absorb the light. This work seeks to obtain the best solvent for the natural dye extraction from Melastoma malabathricum L. seeds. The extracted dye is used as sensitizer on TiO₂ nanoparticles produced via hydrothermal but optimized at relatively low temperature. Infrared characterization of the extracted dyes showed differences in functional groups using different solvents, whereas ultraviolet visible examination of the dyes showed differences in intensity along the spectrum ranges of 600 to 400 nm with maximum absorption around 550 to 500 nm. Thermal analysis revealed that the natural dye should be stable around room temperature. Analysis on the synthesized TiO₂ nanoparticles showed that the average crystallite size reported in the previous work is consistent with crystallite sizes observed in the transmission electron microscope images. Photoactivity examination showed that the DSSC sensitized using natural dye extracted with ethanol containing 20% distilled water on TiO₂ synthesized at 150°C has an efficiency of 5.7%, whereas the one on commercial TiO₂ P25 Degussa has an efficiency of 3.0%. The DSSC device sensitized using commercial dye on TiO₂ synthesized at 150°C has an efficiency of 4.4%, whereas the one on TiO₂ P25 Degussa has an efficiency of 4.0%. This result is promising for further development of the DSSC device using TiO₂ nanoparticles synthesized at low hydrothermal temperature and sensitized with the natural dye.     

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.     

Analysis and assessment of dye‐sensitized solar cell at different materials parameters and environmental conditions

The dye‐sensitized solar cell (DSSC) provides a clean, renewable, and cheap energy source. Since the beginning of the 1990s, DSSC has seen enormous development because of an increase in world energy consumption and the concerns about the environmental impact associated with combustion of fossil fuels. However, the efficiency of the DSSC to be a competitive energy source has not been achieved. In this work, we analyzed the effect of various materials parameters and environmental conditions on the performance of DSSC. To maintain the optimum performance for DSSCs and to enhance the energy and exergy efficiency in practical application environments, it is recommended to have the porous thin film TiO₂ at porosity of 0.40, thin film thickness of porous TiO₂ at 0.0005 cm, thickness of redox electrolyte at 0.0002 cm, diffusion coefficient of 0.0002 cm² s^?1, electron diffusion length of 0.0013 cm, and operating temperature of 300 K with light intensity of 100 mW cm^?2. Copyright © 2016 John Wiley & Sons, Ltd.     

Improved performance of a dye-sensitized solar cell using a TiO2/ZnO/Eosin Y electrode

TiO₂/ZnO/Eosin Y structure films were prepared by a one-step cathodic electrodeposition method and used as a photoanode in a dye-sensitized solar cell (DSSC). Using this TiO₂/ZnO/Eosin Y electrode in DSSC, the degradation of the cell with time was reduced and I_SC, V_OC and fill factor values were increased. The use of a thin ZnO layer, permitted the formation of an energy barrier at the electrode/electrolyte interface, thus reducing recombination rate and improving cell performance. In addition, the adsorbed dye molecules prepared by one-step cathodic electrodeposition with ZnO were very stable compared with that prepared by conventional immersing method, as evidenced by UV/vis absorption spectroscopy measurements.     

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%.     

Recent advances in photo‐anode for dye‐sensitized solar cells: a review

Dye‐sensitized solar cell (DSSC) attracts immense interest in the last few decades due to its various attractive features such as low production cost, ease of fabrication and relatively high conversion efficiency, which make it a strong competitor to the conventional silicon‐based solar cell. In DSSC, photo‐anode performs two important functions, viz. governs the collection and transportation of photo‐excited electrons from dye to external circuit as well as acts as a scaffold layer for dye adsorption. The photo‐anode usually consists of wide band gap semiconducting metal oxides such as titanium dioxide (TiO₂) and zinc oxide (ZnO) deposited on the transparent conducting oxide substrates. The morphology and composition of the semiconductor oxides have significant impact on the DSSC photovoltaic performance. Therefore, enormous research efforts have been undertaken to investigate the influences of photo‐anode modifications on DSSC performance. The modifications can be classified into three categories, namely interfacial modification through the introduction of blocking and scattering layer, doping with non‐metallic anions and metallic cations and replacing the conventional mesoporous semiconducting metal oxide films with one‐dimensional or two‐dimensional nanostructures. In the present review, the previously mentioned modifications on photo‐anode are summarized based on the recent findings, with particular emphasis given to published works for the past 5 years. Copyright © 2017 John Wiley & Sons, Ltd.     

Photovoltage enhancement of dye sensitised solar cells by using ZnO modified TiO2 electrode

Abstract

A ZnO modified TiO₂ (ZnO/TiO₂) film was prepared by immersing TiO₂ electrodes in Zn(Ac)₂ aqueous solution. The open circuit voltage of a dye sensitised solar cell (DSSC) with the ZnO/TiO2 film electrode has a dramatic enhancement, compared to the DSSC with the TiO₂ film electrode. However, the short circuit current density of the DSSC with the ZnO/TiO₂ film electrode is lower than that with TiO₂ electrode. The film electrodes were characterised by SEM, EDX and UV-vis, and the photoelectric performance of DSSCs were measured. The photovoltage enhancement is attributed to the formation of a flat-band potential energy barrier by ZnO at TiO₂/electrolyte interface. The decline of the photocurrent with ZnO/TiO₂ film electrode is due to poor dye absorption on larger particles of ZnO.     

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.     

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.     

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.     

Anchorage of N3 dye-linked polyacrylic acid to TiO2/electrolyte interface for improvement in the performance of a dye-sensitized solar cell

A synthetic route was developed to link N3 dye to polyacrylic acid (PAA) using ethylenediamine (en) as the linker. The resulting complex, PAA–en–N3, was then coated onto a TiO₂ film. The modified TiO₂ film electrode (hereafter PAA–en–N3/TiO₂), when used as the photoanode in a dye-sensitized solar cell (DSSC), exhibited enhanced solar energy conversion efficiency compared with that of the usual DSSC with the N3/TiO₂ film electrode. The increase in efficiency was attributed to the increased open-circuit voltage (V_oc) and short-circuit photocurrent (J_sc). The increase in V_oc was attributed to the formation of a hydrophobic PAA–en–N3 layer on the TiO₂/electrolyte interface, while the increase in J_sc was attributed to the additional dye acquired by the TiO₂ film from the PAA–en–N3 complex.     

Synergistic enhancements in the performances of dye-sensitized solar cells by the scattering and plasmon resonance of Au-nanoparticle multi-shell hollow nanospheres

Novel multi-shell hollow SiO₂@Au@TiO₂ (HSAT) nanospheres are synthesized by multi-step method. Composite photoanodes and Dye-sensitized solar cells (DSSCs) with different amount of HSAT nanospheres are studied. The study indicates that the HSAT nanospheres have enhanced the scattering and absorption of incident light in the photoanode, reduced the interface transmission resistance, increased the electron lifetime, and thus significantly improved performance of DSSCs. The maximal J_sc and photoelectric conversion efficiency (PCE) obtained in the optimal DSSC doped with HSAT of 3.0% are 15.83 mA cm⁻² and 7.21%, greatly enhanced by 21.0% and 20.4%, respectively, compared with those of the pure TiO₂-based DSSC. These remarkable enhancements in DSSCs performance can be attributed to the synergistic and complementary effects of the localized surface plasmon resonance and strong light scattering of HSAT nanospheres, which has significantly improved the absorption and utilization on incident light and thus the PCE of the DSSCs. Such synergistic and complementary effects of the different functions are also likely expected to play roles in the performance improvements in other solar cells.     

Influence of electrolyte on the photovoltaic performance of a dye-sensitized TiO2 solar cell based on a Ru(II) terpyridyl complex photosensitizer

We have investigated the influence of electrolyte composition on the photovoltaic performance of a dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) based on a Ru(II) terpyridyl complex photosensitizer (the black dye). We have also spectroscopically investigated the interaction between the electrolyte components and the adsorbed dye. The absorption peaks attributed to the metal-to-ligand charge transfer transitions of the black dye in solution and adsorbed on a TiO₂ film, were red-shifted in the presence of Li cations, which led to an expansion of the spectral response of the solar cell toward the near-IR region. The photovoltaic performance of the DSSC based on the black dye depended remarkably on the electrolyte composition. We developed a novel efficient organic liquid electrolyte containing an imidazolium iodide such as 1,2-dimethyl-3-n-propylimidazolium iodide or 1-ethyl-3-methylimidazolium iodide (EMImI) for a DSSC based on the black dye. A high solar energy-to-electricity conversion efficiency of 9.2% (J_sc=19.0 mA cm⁻², V_oc=0.67 V, and FF=0.72) was attained under AM 1.5 irradiation (100 mW cm⁻²) using a novel electrolyte consisting of 1.5 M EMImI, 0.05 M iodine, and acetonitrile as a solvent with an antireflection film.     

Tailor and functionalize TiO2 compact layer by acid treatment for high performance dye-sensitized solar cell and its enhancement mechanism

Surface tailoring and functionalization of an annealed TiO₂ compact layer by H₂SO₄ acid was performed to improve the dye-sensitized solar cell (DSSC) performance. Compared to untreated counterpart, the acid-treated compact layer possesses a rougher surface and more hydroxyl groups, which result in increased surface area and enhanced adherence of the compact layer with the mesoporous TiO₂ film by Ti–O–Ti bonds formed by a followed heating process. Impedance measurement was further used to investigate the enhancement mechanism, indicating the acid post treatment of the TiO₂ compact layer reduces the ohmic bulk resistivity while effectively suppressing charge recombination at FTO/electrolyte interface. In DSSCs with untreated TiO₂ compact layer, a significantly increased series resistivity is very likely to be the rate determining factor to limit the charge separation process. Thus, an optimal post acid treatment could reduce the resistivity for high charge transport, resulting in larger short-circuit current for further improvement of power conversion efficiency from 6.60% in DSSC with untreated compact layer to 7.21% in DSSC with acid-treated compact layer. This work also provides fundamental insight of the compact layer for DSSC performance improvement.     

UV light protection through TiO2 blocking layers for inverted organic solar cells

Fully organic solar cells (OSCs) based on polymers and fullerenes have attracted remarkable interest during the last decade and high power conversion efficiencies (PCEs) beyond 8% have been realized. However, air stability of these cells remains poor. The conventional geometry of OSCs utilizes strongly oxidizing metal top contacts like Al or Ca. These metals are easily oxidized in air resulting in rapid decrease of PCE if cells are not perfectly encapsulated. Using a thin electron-selective hole-blocking bottom layer like TiO₂ enables fabrication of solar cells in a so-called inverted geometry. In this geometry, noble metals like Ag or Au can be used as top contacts, which are less sensitive to ambient oxygen. Thus, air-stability of these inverted solar cells is significantly improved. In this study we investigate inverted polythiophene-methanofullerene solar cells. We find significant influence of the TiO₂ layer thickness on light absorption and illumination stability of the solar cells, as well as the trap filling by photoinduced carriers. Even though TiO₂ layers as thick as 500 nm seem not to be detrimental for charge transport, light intensity losses limit the device performance. In turn, illumination stability is better for thicker TiO₂ layers, which can serve as UV filters and protect the photoactive materials from degradation, when compared to thin TiO₂ layers. Considering these different effects we state that a thickness of 100 nm is the optimization of the TiO₂ layer.     

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.     

TiO2 films obtained by microwave-activated chemical-bath deposition used to improve TiO2-conducting glass contact

In traditional solar cells, metal-semiconductor contacts used to extract photogenerated carriers are very important. In dye-sensitized solar cells (DSSC) not much attention has been given to contact between the TiO₂ and the transparent conducting glass (TCO), which is used instead of a metal contact to extract electrons. TiO₂ layers obtained by microwave-activated chemical-bath deposition (MW-CBD) are proposed to improve TiO₂ contact to conducting glass. Spectra of incident photon to current conversion efficiency (IPCE) are obtained for two-photoelectrode TiO₂ photoelectrochemical cells. IPCE spectra show higher values when TiO₂ double layer photoelectrodes are used. In these, the first layer or contacting layer is made by MW-CBD. Best results are obtained for double layer photoelectrodes on FTO (SnO₂:F) as conducting oxide substrate. Modeling of IPCE spectra reveals the importance of electrical contact and electron extraction rate at the TiO₂/TCO interface.     

Highly efficient photon-to-electron conversion with mercurochrome-sensitized nanoporous oxide semiconductor solar cells

Dye-sensitized solar cells based on nanoporous oxide semiconductor thin films such as TiO₂, Nb₂O₅, ZnO, SnO₂, and In₂O₃ with mercurochrome as the sensitizer were investigated. Photovoltaic performance of the solar cell depended remarkably on the semiconductor materials. Mercurochrome can convert visible light in the range of 400–600 nm to electrons. A high incident photon-to-current efficiency (IPCE), 69%, was obtained at 510 nm for a mercurochrome-sensitized ZnO solar cell with an I⁻/I₃⁻ redox electrolyte. The solar energy conversion efficiency under AM1.5 (99 mW cm⁻²) reached 2.5% with a short-circuit photocurrent density (J_sc) of 7.44 mA cm⁻², a open-circuit photovoltage (V_oc) of 0.52 V, and a fill factor (ff) of 0.64. The J_sc for the cell increased with increasing thickness of semiconductor thin films due to increasing amount of dye, while the V_oc decreased due to increasing of loss of injected electrons due to recombination and the rate constant for reverse reaction. Dependence of photovoltaic performance of mercurochrome-sensitized solar cells on semiconductor particles, light intensity, and irradiation time were also investigated. High performance of mercurochrome-sensitized ZnO solar cells indicate that the combination of dye and semiconductor is very important for highly efficient dye-sensitized solar cells and mercurochrome is one of the best sensitizers for nanoporous ZnO photoelectrode. In addition, a possibility of organic dye-sensitized oxide semiconductor solar cells has been proposed as well as one using metal complexes.     

Highly efficient dye-sensitized solar cell prepared by electrophoretic deposition method: the effect of TiO<Subscript>2</Subscript> films thickness on the performance of cells

In this work, nanocrystalline P25 TiO₂ films with different thicknesses were deposited on FTO coated glass substrates by an electrophoretic deposition technique (EPD) and applied as the work electrode for dye-sensitized solar cells (DSSC) using cis-bis(isothiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylato)(4,4'di-nonyl-2'-bipyridyl) ruthenium(II) (Z907, Dyesol) as sensitizing dye.The results showed that the increasing the thickness of TiO₂ films lead to increase the adsorption of the dye on the TiO₂ layers which in turns improved the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. Furthermore, it was found that the effects of the surface states on the recombination of the photo-injected electrons (electron–hole pairs) in the TiO₂ films strongly depend on theTiO₂ electrode annealing temperature. Finally, a DSSC with a 32.82 μm thickness for TiO₂ film annealed at 600°C produced the highest conversion efficiency with an incident solar energy of 100 mW/cm² (η = 8.23%, J_sc = 15.98, V_oc = 0.73, FF = 0.7).     

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.