Degradation mechanisms in a dye-sensitized solar cell studied by UV–VIS and IR spectroscopy

By deliberately causing degradation of components in a dye-sensitized solar cell we have studied failure mechanisms of such cells. The dye, bis(tetrabutylammonium) cis–bis(thiocyanato)bis(2,2^′-bipyridine-4-carboxylic acid, 4^′-carboxylate)ruthenium(II), adsorbed to a nanostructured TiO₂ film was studied with UV–VIS and IR spectroscopy after being exposed to visual and ultra-violet radiation, increased temperature, air, electrolyte, and water in the electrolyte. The thiocyanate ion ligand is lost in air, at temperatures equal to and above 135 °C, in electrolyte and possibly upon UV irradiation. The loss of the SCN⁻ ligand in air was accelerated under visual illumination. From working electrodes immersed in the electrolyte or in degraded complete solar cells it was observed that the absorption peak from the thiocyanate ion ligand at around 2100 cm⁻¹ had broadened, blue-shifted and decreased. One failure mechanism is thus that the thiocyanate ion ligand is lost from the dye together with the electrolyte. Together with water in the electrolyte (5 v%) the SCN⁻ ligand is exchanged with H₂O and/or OH⁻. The ligand exchange between SCN⁻ and H₂O/OH⁻ was accelerated under visual illumination.     

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.     

The use of xylenol orange in a dye-sensitized solar cell

Xylenol orange (3,3′-bis[N,N-di(carboxymethyl)aminomethyl]-o-cresolsulfonephthalein), which is a water-soluble dye of the triphenylmethane group, was tested for a dye-sensitized solar cell. The observed short-circuit current (2.2 mA cm⁻²) was compared with the theoretical value (3.8 mA cm⁻²) which was estimated from the radiation spectrum of light source and the absorption spectrum of adsorbed dye on TiO₂. The overall energy efficiency was 1.3%. The addition of 0.5 M water in the electrolyte did not show a bad effect. A molecule of xylenol orange occupied 1.48 nm² of the TiO₂ surface. The roughness factor of the utilized TiO₂ electrode was 630.     

An analysis of the electrical characteristics of DSC under inhomogeneous solar illumination

A simple model to describe the dye sensitized solar cell (DSC) is presented in which simultaneous occurrence of diffusion and charge transfer processes, power loss due to inhomogeneous excitation resulted from absorption of the dye and the electrolyte, and power gain due to the direct excitation (not via dye molecules) of semiconductor particles are taken into consideration. About 35% and 2.2% decrease in power is estimated for the dye and the electrolyte absorption, respectively, while 2.9% increase of power is obtained by the direct excitation of TiO₂ at maximum power point (MPP) under AM1.5 solar illumination. Some numerical results are also presented to demonstrate the influence of the material parameters for the cell characteristics.     

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.     

Fabrication of solid-state dye-sensitized TiO2 solar cells combined with polypyrrole

A solid-state solar cell was fabricated by photoelectrochemical polymerization of pyrrole on porous nanocrystalline TiO₂ electrode sensitized by the Grätzel dye, cis-di(thiocyanato)-N,N′-bis(2,2′-bipyridyl-4,4′-dicarboxylic acid)-ruthenium (II) dihydrate, [RuL₂(NCS)₂]), or a newly synthesized cis-Ru(dcb)₂(pmp)₂ (pmp=3-(pyrrole-1-ylmethyl)-pyridine). Polypyrrole successfully worked as a hole-transport layer with improvement of the cell characteristics when the TiO₂ cell with cis-Ru(dcb)₂(pmp)₂ was compared with the similarly fabricated cells using [RuL₂(NCS)₂]. The improvement by using Ru(dcb)₂(pmp)₂ can be explained as due to direct molecular wiring of the polymer-chain to the excited metal center of the complex.     

Negative Ames-test of cis-di(thiocyanato)-N,N'-bis(4,4'-dicarboxy-2,2'-bipyridine)Ru(II), the sensitizer dye of the nanocrystalline TiO2 solar cell

Dye-sensitized nanocrystalline TiO₂ solar cells are currently under development. Since these cells contain an electrolyte solution we reviewed the health and safety aspects in view of indoor applications, where personal contact cannot be excluded. Only small amounts of chemicals are present in each cell and so there is no danger of acute toxicity. However, long-term effects often can be caused by incidental contact with minute amounts. For this reason we have tested cis-di(thiocyanato)-bis(4,4′-dicarboxy-2,2′-bipyridine)Ru(II), the sensitizer dye in the Ames test. The dye was not mutagenic in the Salmonella typhimurium reverse mutation assay and in the Escherichia coli reverse mutation assay.     

Stability of the SnO2/MgO dye-sensitized photoelectrochemical solar cell

Dye-sensitized solar cells made of TiO₂ are extensively studied as a cheap alternative to conventional photovoltaic cells. The other familiar stable oxide material of similar band gap suitable for dye sensitization is SnO₂. Although cells based only of SnO₂ are prone to severe recombination losses, the cells made of SnO₂/MgO films where the SnO₂ crystallite is surface covered with an ultra-thin shell of MgO, deliver reasonably high efficiencies. It is found that SnO₂/MgO cells resist dye and electrolyte degradation better than TiO₂ cells. Furthermore, the ultra-thin barrier of MgO on SnO₂ remains intact during prolonged usage or storage of the cell.     

A technique to compare polythiophene solid-state dye sensitized TiO2 solar cells to liquid junction devices

In this communication, we report on a technique to fabricate solid-state polythiophene-based dye sensitized solar cells (DSSCs) that can be directly compared to analogous liquid junction devices. The device configuration is based on non-porous TiO₂ thin films and one of the three undoped polythiophene hole conductors: poly[3-(11 diethylphosphorylundecyl) thiophene], P3PUT, poly(4-undecyl-2,2′-bithiophene), P4UBT, or poly(3-undecyl-2,2′-bithiophene), P3UBT. These polymers were spin coated and cast from organic solutions onto the TiO₂ films. The dense TiO₂ thin films (ca. 30 nm) were deposited on conductive glass via facile spray pyrolysis and sol–gel techniques. After that, cis-(SCN)₂ Bis(2,2′ bipyridyl-4,4′-dicarboxylate) ruthenium(II) (a.k.a. Ru N3 dye) was adsorbed on the TiO₂ surface, and the polythiophenes were utilized as hole conductors in a simplified solar cell geometry. The results were compared to the control DSSC device made with dense TiO₂ and a liquid electrolyte, or 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (a.k.a. Spiro-MeOTAD). The polythiophenes exhibited bandgaps in the range 1.9–2.0 eV, and HOMO energy levels of approximately 5 eV (vs. vacuum). The P3PUT DSSC device exhibited an AM1.5 V_OC=0.8 V, a J_SC=0.1 mA/cm², as well as an IPCE=0.5–1%. The AM1.5 short-circuit photocurrents and quantum efficiencies for DSSCs made with the polythiophenes, the Spiro-MeOTAD and the standard liquid electrolyte (I⁻/I₃⁻) were found to be identical within the limits of experimental uncertainty and reproducibility. Our results indicate that a solid-state replacement to the liquid junction is not necessarily limited by the fundamental aspect of hole transfer, one of the three fundamental aspects that must be met for an efficient DSSC. Rather than suggest that P3UBT or P4UBT could be used to create efficient “organic solar cells” with the exclusion of the Ru dye, we suggest that transparent thiophene compounds could be attractive candidates for high-surface area solid-state DSSCs, and that the technique presented can be applied to other hole conductors. It can allow a verification of one of the things necessary for the DSSC, so that parallel studies using high-surface area materials can proceed with confidence.     

Design of novel efficient sensitizing dye for nanocrystalline solar cell; tripyridine-thiolato (4,,-tricarboxy-2,:,-terpyridine)ruthenium(II)

We have designed tripyridine-thiolato (4,4^′,4^″-tricarboxy-2,2^′:6^′,2^″-terpyridine)ruthenium(II) [complex 1], a novel efficient sensitizing dye for dye sensitized TiO₂ solar cells, based on the DFT MO calculations with PBE0 functional. Complex 1 is a modified BD (black dye: trithiocyanato (4,4^′,4^″-tricarboxy-2,2^′:6^′,2^″-terpyridine)ruthenium(II) complex) molecule where NCS ligands of BD are replaced by C₅H₄NS ligands. Molecular and electronic structures of complex 1 have been theoretically characterized. Complex 1 is expected to have the following two advantages over BD, in addition to the advantage of high electron transfer rate from the photoexcited dye to TiO₂ realized in BD: (1) higher electron transfer rate from redox systems to oxidized dyes; (2) higher absorption efficiency to solar spectrum. We propose complex 1 as a novel efficient sensitizing dye which provides the higher efficiency than does BD for dye sensitized solar cells.     

Performance enhancement of dye‐sensitized solar cells via cosensitization of ruthenizer Z907 and organic sensitizer SQ2

Cosensitization is a highly effective technique to enhance the photovoltaic performance of a dye‐sensitized solar cell. The main objective of this work is to improve the performance of dye‐sensitized solar cell using cosensitization approach and investigation of the effect of the organic cosensitizer concentration on the power conversion efficiency of the fabricated solar cell devices. In this work, Z907, a ruthenium dye, has been cosensitized with SQ2, an organic sensitizer, and an overall efficiency of 7.83% has been achieved. The fabricated solar cells were evaluated using UV‐Vis spectroscopy, current‐voltage (I‐V) characteristics, and electrochemical impedance spectroscopy analysis. Our results clearly indicate that the concentration of organic cosensitizer strongly affects the photovoltaic performance of fabricated solar cells. Upon optimization, the cell fabricated with 0.3 mM Z907 + 0.2 mM SQ2 dye solution demonstrated J_sc (mA/cm²) = 21.38, V_oc (mV) = 698.37, FF (%) = 52.46, and power conversion efficiency of η (%)  = 7.83 under standard AM1.5G 1 sun illumination (100 mW/cm²). It was observed that the efficiency of cosensitized solar cells is significantly superior than that of individual sensitized solar cells (Z907 [η  = 5.08%] and SQ2 [η  = 1.39%]). This enhancement in efficiency could be attributed to the lower electron‐hole recombination rate, decrease in competitive absorption of I^?/I^?₃, and less dye aggregation because of the synergistic effect in cosensitized solar cells.     

Preparation of 1-methyl-3-propylimidazolium acetate and its application in dye sensitized solar cells

In this paper, we reported the preparation of 1-methyl-3-propylimidazolium acetate (MPIAc), which proceeded via the metathesis of 1-methyl-3-propylimidazolium iodide (MPII) and lead acetate or potassium acetate. The apparent diffusion coefficients of triiodide and iodide in binary ionic liquids, MPIAc and MPII with various weight ratios, were demonstrated by cyclic voltammetry using a Pt ultramicroelectrode. It was found that the apparent diffusion coefficients of triiodide increased and those of iodide slightly increased with the weight ratio increase of MPIAc and MPII. The dye sensitized solar cells with the electrolyte, which was composed of 0.13 M I₂, 0.10 M LiI, 0.50 M 4-tert-butylpyrdine in the binary ionic liquid electrolyte of MPIAc (employing potassium acetate) and MPII (weight ratio 0.2), gave short circuit photocurrent density of 9.40 mA cm⁻², open circuit voltage of 0.62 V, and fill factor of 0.57, corresponding to the photoelectric conversion efficiency of 3.34% at the illumination (air mass 1.5, 100 mW cm⁻²).     

Thiocyanate ligand substitution kinetics of the solar cell dye Z-907 by 3-methoxypropionitrile and 4-tert-butylpyridine at elevated temperatures

The dye-sensitized solar cell dye Z-907, [RuLL′(NCS)₂] may loose a thiocyanate ligand at elevated temperatures (80-100 °C) by ligand exchange with the solar cell additive 4-tert-butylpyridine (4-TBP) or the electrolyte solvent 3-methoxypropionitrile (3-MPN). The mechanism in homogeneous solution proceeds via three equilibrium reactions Eqs. (1)-(3) with the solvent complex [RuLL′(NCS)(3-MPN)] as an intermediate:[RuLL′(NCS)₂]+3-MPN=[RuLL′(NCS)(3-MPN)]⁺+NCS⁻ (1)[RuLL′(NCS)(3-MPN)]⁺+4-TBP=[RuLL′(NCS)(4-TBP)]⁺+3-MPN (2)[RuLL′(NCS)₂]+4-TBP=[RuLL′(NCS)(4-TBP)]⁺+NCS⁻ (3)A similar mechanism describes the heterogeneous substitution reactions of Z-907 attached to the surface of TiO₂ particles with 3-MPN and 4-TBP. All the six homogeneous and heterogeneous rate constants were obtained at 100 °C by monitoring the decay of Z-907 and product formation in test-tube experiments by HPLC coupled to UV/vis and electrospray mass spectrometry.A half-lifetime t_1/2=150 h was obtained for the Z-907 dye bound to TiO₂ nanocrystalline particles at 85 °C in the presence of 4-TBP and 3-MPN. Dye-sensitized solar cells (DSC) with Z-907 as a sensitizer and application of the so-called “non-robust” electrolytes containing 4-TBP and 3-MPN is therefore not expected to be able to pass a 1000 h thermal stress test at 85 °C. Addition of thiocyanate to the cell electrolyte may however, eliminate or reduce the problems caused by dye thiocyanate ligand substitution in DSC cells.     

An improved preparation of 3-ethyl-1-methylimidazolium trifluoroacetate and its application in dye sensitized solar cells

In this paper, we reported an improved preparation of 3-ethyl-1-methylimidazolium trifluoroacetate (EMITA), which proceeded via efficient reaction of 1-methylimidazole and ethyl trifluoroacetate under solvent-free conditions using Teflon-lined, stainless steel autoclaves. It was shown that the procedure was simple and eco-friendly. The apparent diffusion coefficients of triiodide and iodide in binary ionic liquids, EMITA and 1-methyl-3-propylimidazolium iodide (MPII) with various weight ratios, were demonstrated by cyclic voltammetry using a Pt ultramicroelectrode. It was found that the apparent diffusion coefficients of triiodide slightly increased and those of iodide decreased with the weight ratio increase of EMITA and MPII. The dye sensitized solar cells with the electrolyte, which was composed of 0.13 M I₂, 0.10 M LiI, 0.50 M 4-tert-butylpyrdine in the binary ionic liquid electrolyte of EMITA and MPII (weight ratio 1:2), gave short circuit photocurrent density of 7.88 mA cm⁻², open circuit voltage of 0.61 V, and fill factor of 0.67, corresponding to the photoelectric conversion efficiency of 3.22% at the illumination (Air Mass 1.5, 100 mW cm⁻²).     

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).     

An effective use of nanocrystalline CdO thin films in dye-sensitized solar cells

Thin films of cadmium oxide (CdO) were synthesized by layer-by-layer deposition method on indium doped tin oxide (ITO) substrates. Post-deposition annealing at 250 °C for 24 h produced pure phase CdO films by removal of trace amount of cadmium hydroxide, as confirmed from X-ray diffractogram. First time employment of CdO in place of TiO₂ in dye-sensitized solar cells is reported to check feasibility and cell performance. A dye-sensitized nanocrystalline CdO photo-electrode was obtained by adsorbing cis-dithiocyanato (4,4′-dicarboxylic acid-2,2′-bipyridide) ruthenium (II) (N3) dye by keeping at 45 °C for 20 h. The efficiency of dye-sensitized nanocrystalline CdO thin film solar cell was increased from 0.24% to 2.95% due to dye adsorption. This must be highest reported conversion efficiency for other metal oxides than TiO₂based dye-sensitized solar cells.     

Photoelectric behavior of nanocrystalline TiO2 electrode with a novel terpyridyl ruthenium complex

The photoelectric behavior of a black dye, tris (isothiocyanato)-[N-(2,2′:6′,2″-terpyridine-4′-(4-carboxylic acid) phenyl)] ruthenium (II) complex, was examined under different conditions. The dye was adsorbed on nanocrystalline TiO₂ surface strongly and generated incident monochromatic photon-to-current conversion efficiency (IPCE) of about 90% at maximum absorption wavelength and greater than 20% in the near-IR region. A sandwich-type solar cell fabricated by this dye-sensitized nanocrystalline TiO₂ film generated 6.1 mAcm⁻² of short-circuit photocurrent, 0.58 V of open-circuit photovoltage and 2.9% of overall yield under irradiation of white light (78.0 mWcm⁻²) from a Xe lamp. Since the title dye shows better photoresponse than the N3 dye in the near-IR region, it would be a promising panchromatic sensitizer after optimization.     

The effect of a blocking layer on the photovoltaic performance in CdS quantum-dot-sensitized solar cells

In order to reduce the surface recombination at the interface between the fluorine-doped tin oxide (FTO) substrate and the polysulfide electrolyte in CdS quantum-dot-sensitized solar cells (QDSCs), compact TiO₂ is deposited on the FTO electrode by sputtering. The TiO₂-coated CdS-sensitized solar cell exhibits enhanced power-conversion efficiency (0.52%) compared with a bare CdS-sensitized solar cell (0.23%). Charge-transfer kinetics are analyzed by impedance spectroscopy, open-circuit decay, and cyclic voltammetry. The TiO₂ layer deposited on the FTO substrate acts as a blocking layer, which plays a significant role in reducing the electron back transfer from the FTO to the polysulfide electrolyte. Interestingly, with respect to the incident photon-to-current conversion efficiency (IPCE) data, asymmetric enhancement is observed from the sample with a thicker blocking layer. This is because CdS quantum dots absorb ultraviolet light completely with the TiO₂ layer because of the high extinction coefficient of the CdS quantum dots compared with dye molecules.     

Highly efficient solid-state dye-sensitized TiO2 solar cells via control of retardation of recombination using novel donor-antenna dyes

Two series of heteroleptic tris(bipyridyl)Ru(II) and bis(bipyridyl)(NCS)₂Ru(II) complexes have been synthesized and characterized. This is a part of a new concept of covalent linkage of donor-antenna groups, e.g., triphenylamine or N,N′-bis(phenyl)-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD) to Ru(II) dye center. For the covalent attachment of donor units, a multi-step synthesis was carried out starting from 4,4′-dimethyl-2,2′-bipyridine followed by chlorination and Wittig reaction with donor aldehydes. This was followed either by a metallation reaction using bis(4,4′-dicarboxy-2,2′-bipyridyl)Ru(II)dichloride ((bpy(COOH)₂Ru(II)2Cl₂ 2H₂O) as precursor to get tris(bipyridyl) dyes or by a one pot synthesis starting from dichloro(p-cymene)Ru(II) dimer resulting in bis(bipyridyl)(NCS)₂ dyes. The complexes (bpy(COOH)₂)₂(bpyMe₂)Ru(II) 2PF₆ and (bpy(COOH)₂)(bpyMe₂)(NCS)₂Ru(II) without donor-antenna groups were also prepared to study and compare the properties. The influence of donor-antenna groups in these complexes was studied using UV–Vis spectroscopy and cyclic voltammetry. The heteroleptic complexes carrying donor groups show appreciably broad absorption ranges and extraordinarily high extinction coefficients. These high extinction coefficients are explained as due to the extended delocalization of π-electrons in the donor-antenna ligands. The HOMO/LUMO energy values obtained from cyclic voltammetry support the multi-step charge transfer cascade possible in these donor-antenna dyes. Examples of solid-state dye-sensitized solar cell utilizing these novel donor-antenna dyes revealed spectacular performances of power conversion efficiencies of up to 3.4%, for the dye carrying a TPD donor group as measured under AM 1.5 spectral conditions. This is attributed to highly efficient light harvesting of these novel dyes and the improved charge transfer dynamics at TiO₂–dye and dye–hole conductor interfaces.     

A dye sensitized TiO2 photovoltaic cell constructed with an elastomeric electrolyte

A photovoltaic solar cell employing an elastomeric electrolyte and using a dye-sensitized nanoporous TiO₂ electrode has been assembled. The polymeric electrolyte is poly(epichlorohydrin-co-ethylene oxide) filled with NaI/I₂. This cell exhibits an open-circuit voltage of 0.71 V and a short-circuit current of 0.46 mA cm⁻² under 120 mW cm⁻² of white-light illumination. The overall conversion efficiency of the cell is 0.22%. The polymeric electrolyte behavior under different conditions of external resistance and intensity of light as well as the performance of this photoelectrochemical cell are discussed.