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.     

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.     

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.     

Mix-solvent-thermal method for the synthesis of anatase nanocrystalline titanium dioxide used in dye-sensitized solar cell

Nanocrystalline TiO₂ with almost pure anatase form has been synthesized through the Mix-solvent-thermal method (MST) by using TiCl₄ as the starting material. The mean size of the synthesized TiO₂ is 10 nm with narrow distribution. High-performance dye-sensitized solar cell with nanocrystalline TiO₂ electrode formed from MST was achieved. Its I_sc and V_oc values reached 21.62 mA/cm² and 727.9 mV, respectively, and the photovoltaic conversion efficiency reached 9.13%, i.e. 7.5% higher than those of solar cells with TiO₂ made from the traditional precursor of titanium alkoxides. To our knowledge they are the highest values obtained from the solar cells with nanocrystalline TiO₂ electrode formed from the hydrolysis of TiCl₄.     

Highly efficient 1 μm thick CdTe solar cells with textured TCOs

Thickness reduction of CdTe absorption layer down to 1 μm has been achieved by controlling the temperature profile used during the close-spaced sublimation (CSS) growth. Transparent conducting oxides, such as indium tin oxide (ITO) and textured fluorine doped tin oxide (SnO₂:F) films have been investigated as transparent electrodes for such 1-μm-thick CdTe absorption layers to increase the incident light confinement and thus to achieve higher conversion efficiency. The contribution in solar cell performance has been found in the case of textured TCOs with optimum haze ratio (roughness). Conversion efficiencies of 10.6% (V_oc: 0.75 V, J_sc: 22.02 mA/cm², FF: 0.64, area: 1 cm²) and 11.2% (V_oc: 0.78 V, J_sc: 22.6 mA/cm², FF: 0.63) have been achieved for only 0.6-μm-thick CdTe absorption layers with SnO₂:F-TCO of 11% and 3% of haze ratios, respectively.     

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.     

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.     

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.     

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%).     

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 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.     

DFT investigation of the TiO2 band shift by nitrogen-containing heterocycle adsorption and implications on dye-sensitized solar cell performance

A density functional theory (DFT) method (periodic DMol³) with full geometry optimization was used to investigate the adsorption of nitrogen-containing heterocycles such as 4-t-butylpyridine (TBP) and imidazole on a TiO₂ anatase (1 0 1) surface. Negative shifts of the TiO₂ Fermi level by N-containing heterocycle adsorption were observed. Imidazole adsorption shifted the Fermi level of TiO₂ more negatively than TBP. This shift corresponded to the enhancement of the open-circuit photovoltage (V_oc) and the reduction of the short-circuit photocurrent density (J_sc) in a dye-sensitized TiO₂ solar cell. We are the first to theoretically discover a TiO₂ band shift upon N-containing heterocycles adsorption, and have successfully related this shift to the effect as an additive in an electrolyte solution on dye-sensitized solar cell performance.     

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 solar cells on paper substrates

This article reports for the first time in the literature, a dye sensitized solar cells with 1.21% efficiency (V_oc=0.56 V, J_sc=6.70 mA/cm² and F.F.=0.33) on paper substrates. The current dye sensitized solar cell technology is based on fluorine doped SnO₂ (FTO) coated glass substrates. The problem with the glass substrate is its rigidity and heavy weight. Making DSSCs on paper opens the door for both photovoltaic and paper industries. The potential of using mature paper making and coating technologies will greatly reduce the current PV cost. Paper substrate based DSSCs not only offer the advantages of flexibility, portability and lightweight but also provide the opportunities for easy implantation to textile. In this study, a low temperature process is developed to coat uniform nickel on paper substrate as the metal contact to replace the traditional expensive FTO. The Ni paper showed excellent conductivity of 8-10 Ω/□. It is found that the control of metal oxide electrode morphology is critical to solar cell performance. The TiO₂ film has the tendency to crack on Ni coated paper, which resulted in the shunt of the device and no solar cell efficiency was obtained. ZnO film on the other hand had good morphology tolerance on Ni coated paper and yielded solar cell efficiency of 1.21% (V_oc=0.56 V, J_sc=6.70 mA/cm² and F.F.=0.33) under AM 1.5 (activation area is 0.16 cm²). The control sample of ZnO solar cell on FTO glasses has the efficiency of 2.66% (V_oc=0.64 V, J_sc=9.97 mA/cm² and F.F.=0.42).     

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.     

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.     

Improved Jsc in CIGS thin film solar cells using a transparent conducting ZnO:B window layer

A comparative study of the cell performance of CIGS thin-film solar cells fabricated using ZnO:Al and ZnO:B window layers has been carried out. ZnO:B films were deposited by RF magnetron sputtering using an undoped ZnO target in a B₂H₆–Ar gas mixture. The short-circuit current (J_sc) was found to improve upon the replacement of the ZnO:Al layer with ZnO:B layers. This improvement in J_sc is attributed to an increase in quantum efficiency due to the higher optical transmission of the ZnO:B layer in the near-infrared region. The best cell fabricated with a MgF₂/ZnO:B/i-ZnO/CdS/CIGS/Mo structure yielded an active area efficiency of 18.0% with V_oc=0.645 V, J_sc=36.8 mA/cm², FF=0.76, and an active area of 0.2 cm² under AM 1.5 illumination.     

Series-connected tandem dye-sensitized solar cell for improving efficiency to more than 10%

As one of the methods for improving the efficiency of a dye-sensitized solar cell (DSC), we investigated series-connected tandem DSCs. In this system, the top cell is made up of a transparent cell and the bottom cell utilizes only the light passing through the top cell. We investigated several combinations of dyes in tandem-type DSCs. The best efficiency obtained in our study is 10.4% (J_sc=10.8 mA/cm², V_oc=1.45 V, and FF=0.67) for a series-connected tandem DSC consisting of an N719 top cell and a black-dye bottom cell.     

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.     

Large area thin film Si module

An initial efficiency of 14.1% (J_sc=13.6 mA/cm², V_oc=1.392 V, FF=74.3%) has been achieved for a-Si/transparent interlayer/poly Si solar cell (total area of 1 cm²). Both a-Si and crystalline Si films were fabricated by plasma chemical deposition at low temperature. The short circuit current was enhanced by the introduction of a transparent intermediate layer. An initial aperture efficiency of 11.7% has been achieved for 910×455 mm² a-Si/poly Si integrated solar cell submodule, where the laser-scribing techniques were applied for series interconnections. The results of our first run of 266 submodules in our pilot plant showed the average efficiency of 11.2%, which is applicable for mass production.