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.     

Manufacturing method for transparent electric windows using dye-sensitized TiO2 solar cells

The transparent electric windows based on dye-sensitized nanocrystalline TiO₂ solar cells have been prepared. The solar cell consists of dye-sensitized TiO₂ electrode with a TiO₂ layer of an about 8 μm thickness and of a 80×80 mm² active area, Pt counter electrode and redox electrolyte. The solar cell shows a transmittance of approximately 60% in the visible range and an open-circuit voltage (V_oc) of 0.64 V and a short-circuit photocurrent (J_sc) of 250 mA. A moderately transparent electric window composed of nine unit solar cells in series generates V_oc of 5.7 V and J_sc of 220 mA at one sun light intensity.     

On the use of triethylamine hydroiodide as a supporting electrolyte in dye-sensitized solar cells

For the first time, the application of a molten salt, triethylamine hydroiodide (THI), as a supporting electrolyte was investigated for the dye-sensitized solar cells (DSSCs). Titanium dioxide (TiO₂) electrode was modified by incorporation of high- and low-molecular weight poly(ethylene glycol) along with TiO₂ nanoparticles of two different sizes (300 nm (30 wt%) and 20 nm (70 wt%)). The highest apparent diffusion coefficient (D) of 8.12×10⁻⁶ cm² s⁻¹ was obtained for I⁻ (0.5 M of THI) from linear sweep voltammetry (LSV). Short-circuit current density (J_sc) increases with the concentration of THI whereas open-circuit potential (V_oc) remains the same. Optimum J_sc (19.28 mA cm⁻²) and V_oc (0.7 V) with a highest conversion efficiency (η) of 8.45% were obtained for the DSSC containing 0.5 M of THI/0.05 M I₂/0.5 M TBP in CH₃CN. It is also observed that the J_sc and η of the DSSC mainly relates with the D values of I⁻ and charge-transfer resistances such as R_ct1 and R_ct2 operating along Pt/TiO₂ electrolyte interface, obtained from LSV and electrochemical impedance spectroscopy (EIS). For comparison, tetraethylammonium iodide (TEAI) and LiI were also selected as supporting electrolytes. Though both the THI and TEAI have similar structures, replacement of one methyl group by hydrogen improves the efficiency of the DSSC containing the former electrolyte. Further, the DSSC containing THI exhibits higher J_sc and η than LiI (7.70%), from which it is concluded that THI may be used as an efficient and alternative candidate to replace LiI in the current research of DSSCs.     

Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes

We have developed dye-sensitized nanocrystalline TiO₂ solar cells (DSSCs) based on novel coumarin-dye photosensitizers. The absorption spectra of these novel dyes are red-shifted remarkably in the visible region relative to the spectrum of C343, a conventional coumarin dye. Introduction of a methine unit (–CH=CH–) connecting the cyano (–CN) and carboxyl (–COOH) groups into the coumarin framework expanded the π-conjugation in the dye and thus resulted in a wide absorption in the visible region. These novel dyes performed as efficient photosensitizers for DSSCs. A DSSC based on 2-cyano-5-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-penta-2,4-dienoic acid (NKX-2311), produced a 6.0% solar energy-to-electricity conversion efficiency (η), the highest performance among DSSCs based on organic-dye photosensitizers, under AM 1.5 irradiation (100 mW cm^–2) with a short-circuit current density (J_sc) of 14.0 mA cm^–2, an open-circuit voltage (V_oc) of 0.60 V, and a fill factor of 0.71. Our results suggests that the structure of NKX-2311 whose carboxyl group is directly connected to the –CH=CH– unit, is advantageous for effective electron injection from the dye into the conduction band of TiO₂. In addition, the cyano group, owing to its strong electron-withdrawing ability, might play an important role in electron injection in addition to a red shift in the absorption region. On a long-term stability test under continuous irradiation with white light (80 mW cm^–2), stable performance was attained with a solar cell based on the NKX-2311 dye with a turnover number of 2.6×10⁷ per one molecule.     

Design of high-efficiency solid-state dye-sensitized solar cells using coupled dye mixtures

A solid-state dye-sensitized solar cell comprising dye mixtures of [Ru(2,2-bpy-4,4′-dicarboxylic acid)(NCS)₂] and [Ru(4,4′,4″-tricarboxy-2,2;6,2″-terpy)(NCS)₃] on TiO₂ thin film was fabricated. The different optical properties of dyes results in increased photocurrent and incident photon to photocurrent efficiency (IPCE). The multiple dye system showed the short circuit current (I_sc) of 10.2 mA/cm² and a cell efficiency (η) of 2.8 while broadening the spectral sensitivity of the cell. When a single dye is used, I_sc of 6 and 5 mA/cm² and cell efficiency of 1.7 and 1.2 were observed for [Ru(4,4-bis(carboxy)-bpy)₂(NCS)₂] (dye 1) and [Ru(2,2′,2″-(COOH)₃-terpy)(NCS)₃] (dye 2), respectively. Additionally, the resulting IPCE for the solar cell consisting of dye mixture was 50% at wide wavelength range from 530 to 650 nm while for the dye 1, 32% IPCE was observed at 535 nm while for the dye 2, highest IPCE value observed was 20% at 620 nm.     

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.     

Facile fabrication of mesoporous TiO2 electrodes for dye solar cells: chemical modification and repetitive coating

A chemical dispersing technique for preparing a coating paste of TiO₂ nanoparticles is disclosed to fabricate mesoporous electrodes for dye-sensitized TiO₂ solar cells. The suspension of TiO₂ (P-25) powder was stirred in aqueous nitric acid at 80°C, and then evaporated to dryness, giving the nitric acid-adsorbed P-25 powder. The coating paste was obtained by mixing the nitric acid-adsorbed P-25 with PEG (M_w 20,000) as a porosity-controlling agent and cellulosic polymer as a thickener. The mesoporous TiO₂ films were fabricated on conducting glasses by repetitive coating and calcined at 500°C (30 min). The TiO₂ film obtained by the five times repetitive coating (20 μm thickness) resulted in the 1.4 times higher energy conversion efficiency of the dye-sensitized solar cells than that of the one time coating TiO₂ film (V_oc=690 mV, J_sc=12.2 mA/cm², the fill FACTOR=0.71 and η=6.0%).     

The influence of surface morphology of TiO2 coating on the performance of dye-sensitized solar cells

The optimization of solar energy conversion efficiency of dye-sensitized solar cells (DSSCs) was investigated by the tuning of TiO₂ photoelectrode's surface morphology. Double-layered TiO₂ photoelectrodes with four different structures were designed by the coating of TiO₂ suspension, incorporated with low and high molecular weight poly(ethylene glycol) as a binder. Among these four systems, P2P1, where P1 and P2 correspond to the molecular weight of 20,000 and 200,000, respectively, showed the highest efficiency under the conditions of identical film thickness and constant irradiation. This can be explained by the larger pore size and higher surface area of P2P1 TiO₂ electrode than the other materials as revealed by scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analyses. Electrochemical Impedance Spectroscopy (EIS) analysis shows that P2P1 formulation displayed a smaller resistance than the others at the TiO₂/electrolyte interface. The best efficiency (η) of 9.04% with the short-circuit photocurrent density (J_sc) and open-circuit voltage (V_oc) of 18.9 mA/cm² and 0.74 V, respectively, was obtained for a solar cell by introducing the light-scattering particles to the TiO₂ nanoparticles matrix coated on FTO electrode having the sheet resistivity of 8 Ω/sq.     

Dye-sensitized solar cell based on Rose Bengal dye and nanocrystalline TiO2

Dye-sensitized solar cell is fabricated using Rose Bengal dye (RB) for sensitization of nanocrystalline TiO₂ and that imparts extension in spectral response towards visible region by modifying the semiconductor surface. Further, the photoresponse of the cell was evaluated by analyzing its J–V and impedance characteristics under illumination with metal halide light source of 400 W with an incident light of 73 mW/cm². Various photovoltaic parameters like J_sc, V_oc, FF were evaluated and found to be 3.22 mA, 890 mV, 0.53, respectively, resulting conversion efficiency (η) of 2.09%. Impedance analysis of the cell was carried out to investigate the internal resistance of the cell by recording Cole–Cole plots in between real and imaginary impedance in dark and with illumination under variable biasing, i.e. from 0 to 3 V.     

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.     

Study on squarylium cyanine dyes for photoelectric conversion

For photoelectric conversion, three of squarylium cyanine dyes were synthesized and their photoelectrochemical parameters were improved with increase in the adsorption ability of the dyes on nanocrystalline TiO₂. A relatively high photoelectric conversion efficiency of 2.17% and the top incident photon-to-photocurrent conversion efficiency of 6.2% at 650 nm for the dye of highest adsorption ability among the three were obtained. Meanwhile, doping cis-Ru[4,4′-(LL)]₂ (NCS)₂ with 1% of the above-mentioned dye (molar ratio) as a photosensitizer, the photoelectrochemical solar cell made an efficient complement to light-harvesting capacity in almost the whole visible range with the photoelectric conversion efficiency increasing by 12% relative to that of pure cis-Ru[4,4′-(LL)]₂ (NCS)₂ (L=2,2′-bipyridyl-4,4′-dicarboxylate).     

Influence of electrolytes on the photovoltaic performance of organic dye-sensitized nanocrystalline TiO2 solar cells

We have studied the influence of electrolytes on the photovoltaic performance of mercurochrome-sensitized nanocrystalline TiO₂ solar cells using LiI, LiBr, and tetraalkylammonium iodides as the electrolyte. Short-circuit photocurrent density (J_sc) and open-circuit photovoltage (V_oc) depended strongly on the electrolyte. J_sc of 3.42 mA cm⁻² and V_oc of 0.52 V were obtained for the LiI electrolyte and J_sc of 2.10 mA cm⁻² and V_oc of 0.86 V were obtained for the Pr₄NI electrolyte. This difference in photovoltaic performance was due to the change in the conduction band level of the TiO₂ electrode. Large V_oc of 0.99 V was obtained for the LiBr electrolyte due to the large energy gap between the conduction band level of TiO₂ and the Br/Br₂ redox potential. Solar cell performance also depended strongly on organic solvent, suggesting that the physical properties of solvents such as Li ion conductivity and donor number affect photovoltaic performance.     

Influence of pyrazole derivatives in I/I3 redox electrolyte solution on Ru(II)-dye-sensitized TiO2 solar cell performance

The influence of pyrazole additives in an I⁻/I₃⁻ redox electrolyte solution on the performance of a bis(tetrabutylammonium)cis-bis(thiocyanato)bis(2,2′-bipyridine-4-carboxylic acid, 4′-carboxylate)ruthenium(II) (N719) dye-sensitized TiO₂ solar cell was studied. The current–voltage characteristics of the cell were measured using 18 different pyrazole derivatives. All of the pyrazole additives enhanced the open-circuit photovoltage (V_oc) and the solar energy conversion efficiency (η), but reduced the short-circuit photocurrent density (J_sc). Most of the pyrazoles improved fill factor (ff). The physical and chemical properties of the pyrazoles were computationally calculated in order to elucidate the reasons for the additive effects on cell performance. The greater the partial charge of the nitrogen atom at position 2 in the pyrazole group, the larger the V_oc, but the smaller the J_sc values. As the dipole moment of the pyrazole derivatives increased, the V_oc value increased, but the J_sc value decreased. The V_oc of the cell also increased as the ionization energy of the pyrazoles decreased. These results suggest that the electron donicity of the pyrazole additives affected the interaction with the nanocrystalline TiO₂ photoelectrode, the I⁻/I₃⁻ electrolyte, and the acetonitrile solvent, which changed the Ru(II)-dye-sensitized solar cell performance.     

Temperature dependence and the oscillatory behavior of the opto-electronic properties of a dye-sensitized nanocrystalline TiO2 solar cell

A dye-sensitized TiO₂ solar cell was developed and characterized. The I–V (current–voltage) characteristics were studied at different temperatures from −40°C to 80°C. The opto-electronic properties of the cell depend on factors like ambient temperature and the time constants of the redox processes at the cell interfaces. The temperature dependence of V_oc and I_sc were clearly demonstrated. I_sc increased with increasing temperature above room temperature, where as V_oc increased with decreasing temperature below room temperature. The opto-electronic properties showed oscillatory behavior especially at low temperatures, which may be attributed to the different velocities of the redox processes occurring at the TiO₂/dye, dye/electrolyte and the electrolyte/counter electrode interfaces.     

Influence of alkyl dihalide gelators on solidification of dye-sensitized solar cells

Quasi-dye-sensitized solar cells were prepared by using ionic liquid-type electrolytes and gelators consisting of polyvinylpyridine and alkyl dihalides. Gelation occurred by the reaction of polyvinylpyridine and alkyl dihalides. When the chain length of the dihalides was varied, the short-circuit current (J_sc) increased with an increase in the chain length. However, the open-circuit voltage (V_oc) and fill factor (ff) slightly decreased. The increase in J_sc was brought about by the decrease in the interfacial resistances between the gel electrolyte and the counter electrode. In addition, the increase in the J_sc was explained by increases in the apparent diffusion coefficient of I⁻/I₃⁻ when the chain length increased. Decreases in V_oc and ff were explained by back-electron transfers from TiO₂ to iodine in the electrolytes. V_oc of the cells solidified by alkyldiiodide was lower than that solidified by alkyldichloride or alkyldibromide. It was explained by negatively shifted redox potential of I⁻/I₃⁻, compared with those for Cl⁻/Cl₂ or Br⁻/Br₂.     

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.     

Blue sensitizers for solar cells: Natural dyes from Calafate and Jaboticaba

Blue-violet anthocyanins from Jaboticaba (Myrtus cauliflora Mart) and Calafate (Berberies buxifolia Lam) were employed as TiO₂ dye-sensitizers. Solar cells sensitized by Jaboticaba extracts achieved up to J_sc=9.0 mA cm⁻², V_oc=0.59 V, P_max=1.9 mW cm⁻² and ff=0.54, while for Calafate sensitized cells the values determined were up to J_sc=6.2 mA cm⁻², V_oc=0.47 V, P_max=1.1 mW cm⁻² and ff=0.36. Other natural dyes were evaluated without significant photocurrent, demonstrating that only selected extracts are capable of converting sunlight in electricity. The results obtained with extracts of Jaboticaba and Calafate show a successful conversion of visible light into electricity by using natural dyes as wide band-gap semiconductor sensitizers in dye-sensitized solar cells. It also represents an environmentally friendly alternative for dye-sensitized solar cells with low cost production and an excellent system for educational purposes.     

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).     

Influence of alkylaminopyridine additives in electrolytes on dye-sensitized solar cell performance

The influence of alkylaminopyridine additives on the performance of a bis(tetrabutylammonium)cis-bis(thiocyanato)bis(2,2′-bipyridine-4-carboxylic acid, 4′-carboxylate)ruthenium(II) dye-sensitized TiO₂ solar cell with an I⁻/I₃⁻ redox electrolyte in acetonitrile was studied. The current–voltage characteristics were measured for more than 20 different alkylaminopyridines under AM 1.5 (100 mW/cm²). The alkylaminopyridine additives tested had varying effects on the performance of the cell. All the additives decreased the short circuit photocurrent density (J_sc), but increased the open-circuit photovoltage (V_oc) of the solar cell. Molecular orbital calculations imply that the dipole moment of the alkylaminopyridine molecules influences the J_sc of the cell and that the size, solvent accessible surface area, and ionization energy all affect the V_oc of the cell. The highest V_oc of 0.88 V was observed in an electrolyte containing 4-pyrrolidinopyridine, which is comparable to the maximum V_oc of 0.9 V for a cell consisting of TiO₂ electrode and I⁻/I₃⁻ redox system.     

Red Sicilian orange and purple eggplant fruits as natural sensitizers for dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were assembled by using red Sicilian orange juice (Citrus Sinensis) and the purple extract of eggplant peels (Solanum melongena, L.) as natural sensitizers of TiO₂ films. Conversion of solar light into electricity was successfully accomplished with both fruit-based solar cells. The best solar energy conversion efficiency (η=0.66%) was obtained by red orange juice dye that, under AM 1.5 illumination, achieved up to J_sc=3.84 mA/cm², V_oc=0.340 V and fill factor=0.50. In the case of the extract of eggplant peels, the values determined were up to J_sc=3.40 mA/cm², V_oc=0.350 V and fill factor=0.40. Cyanidine-3-glucoside (cyanine) and delphinidin 3-[4-(p-coumaroyl)-l-rhamnosyl(1-6)-glucopyranoside]-5-glucopyranoside (nasunin) are the main pigments of cocktail dyes for red orange and eggplant, respectively. Actually, their application is far below the industrial requirements. Nevertheless, their study is an interesting multidisciplinary exercise useful for dissemination of knowledge and to educate people on renewable energy sources. Here, we report and discuss the role of the structure, the absorption spectra and the sensitization activity of the mentioned compounds.