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.     

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.     

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.     

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).     

Enhancement in the performance of dye-sensitized solar cells containing ZnO-covered TiO2 electrodes prepared by thermal chemical vapor deposition

A ZnO-covered TiO₂ (denoted as ZnO/TiO₂) film was prepared by incorporating a small quantity of particulate ZnO in a TiO₂ matrix by thermal chemical vapor deposition. When used in a dye-sensitized solar cell, an enhancement was observed in both short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc) by 12% and 17%, respectively, relative to those of a cell containing a bare TiO₂ film. The observed J_sc enhancement is attributed to the increase in the surface area of the ZnO/TiO₂ film, and the V_oc enhancement to the formation of a potential barrier by ZnO at TiO₂/electrolyte interface. The films were characterized by FE-SEM, EDX, and XRD.     

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.     

A comparison of fluorine tin oxide and indium tin oxide as the transparent electrode for P3OT/TiO2 solar cells

Open circuit voltage (V_oc) and other photovoltaic parameters from fluorine tin oxide (FTO) P3OT/TiO₂ composite solar cells have been investigated in comparison with those from the indium tin oxide (ITO) devices with the same device structure and fabrication process. From the experimental results, the performance of FTO-based devices is better than that of ITO devices in terms of V_oc, short circuit current density (J_sc), and power conversion efficiency. The origin of V_oc and the higher V_oc of FTO can be explained and estimated by metal–insulator–metal model with a non-ohmic cathode contact.     

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.     

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

The influence of aminothiazole additives in acetonitrile solution of an I⁻/I₃⁻ redox electrolyte 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 were investigated under AM 1.5 (100 mW/cm²) for nine different aminothiazole compounds. The aminothiazole additives tested had varying influences on the solar cell performance. Most of the additives enhanced the open-circuit photovoltage (V_oc), but reduced the short circuit photocurrent density (J_sc) of the solar cell. Both the physical and chemical properties of the aminothiazoles were computationally calculated in order to determine the reasons that the additive influenced solar cell performance. The larger the calculated partial charge of the nitrogen atom in the thiazole, the higher the V_oc value. The V_oc value increased as the dipole moment of aminothiazoles in acetonitrile increased. Moreover, the V_oc of the solar cell also increased as the size of the aminothiazole molecules decreased. These results suggest that the electron donicity of the aminothiazole additives influenced the interaction with the TiO₂ photoelectrode, which altered the dye-sensitized solar cell performance.     

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.     

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.     

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.     

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.     

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.     

Effects of pH of a hybrid gel incorporated with 3-aminopropyltrimethoxysilane on the performance of a quasi-solid state dye-sensitized solar cell

Network hybrid gel prepared with tetraethyl orthosilicate, 3-aminopropyltrimethoxysilane (APS) and poly(ethylene glycol) was used as an electrolyte matrix in a quasi-solid state dye-sensitized solar cell (DSSC). Change in pH of this hybrid gel by varying the composition of APS was found to have remarkable effects on the photoelectrochemical performance of the cell. The hybrid gel matrix, having silane polymer backbones with free amine functionality, was characterized by FT-IR spectra and FE-SEM images, and the assembled DSSC by photocurrent-voltage and incident photon to current conversion efficiency curves. The unsealed, quasi-solid state DSSC with the hybrid gel has shown an increase in the open-circuit voltage (V_oc) and a steady decrease in the short-circuit photocurrent (J_sc), with increase in the content of APS. A maximum conversion efficiency of 4.5% was obtained for a DSSC by using 20% of APS in its hybrid gel at a light intensity of 100 mW cm⁻². Upon replacing the amino group of APS by bulkier aniline and benzophenoaniline groups, conversion efficiencies of the corresponding DSSCs were reduced. Variations in the V_oc and J_sc are explained in terms of shift of the flat band potential of TiO₂ and a complex formation between I₃⁻ and −NH₂ of APS of the electrolyte.     

High-efficiency CIGS solar cells with modified CIGS surface

CIGS films were treated in In–S aqueous solution for high-efficiency CIGS solar cells. The In–S aqueous solution contained InCl₃ and CH₃CSNH₂ (thioacetamide). The In–S treatment modified the CIGS surface favorably for high-efficiency CIGS solar cells as evidenced by the increase in V_oc, J_sc and FF. The In–S treatment formed thin CuInS₂ layer on the CIGS surface which contributes to the high efficiency and stable performance of the CIGS solar cell. The best cell showed an efficiency of 17.6% (V_oc=0.649 V, J_sc=36.1 mA/cm² and FF=75.1%) without any annealing and light soaking before I–V measurement.     

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.     

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.     

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.