High molar extinction coefficient heteroleptic ruthenium complexes for thin film dye-sensitized solar cells

Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)2 and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'-bipyridine) (NCS)2, coded as K-19 and K-73, respectively, have been synthesized and characterized by 1H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m2 intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS).     

A new 1H-pyridin-(2E)-ylidene ruthenium complex as sensitizer for a dye-sensitized solar cell

The new heteroleptic ruthenium(II) complex containing a 1H-pyridin-(2E)-ylidene (PYE) ligand was synthesized and characterized using UV/Vis, FTIR, and NMR spectroscopies, mass spectrometry, elemental analysis, and cyclic voltammetry. The photovoltaic performance of the ruthenium complex as a charge transfer photosensitizer in nc-titanium dioxide based dye-sensitized solar cell was studied and compared with cis-bis(isothiocyanato)(2,2′-bipyridyl-4,4′-dicarboxylato)(2,2′-bipyridyl-4,4′-di-nonyl)ruthenium(II) (Z907) under standard AM 1.5 sunlight. The complex CS90 gave a photocurrent density of 1.80?mA?cm^?2, 400?mV open-circuit potential, and 0.58 fill factor yielding an efficiency of 0.42% where the reference Z907 yielded an efficiency of 4.12%. The decrease in conversion efficiency observed for CS90 is attributed to a steric interaction between PYE and the TiO₂ surface that prevents optimum binding and also restricts ligand dynamics that are associated with oxidation state changes.     

Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached. Along with an acetonitrile-based electrolyte, the C101 sensitizer has already achieved a strikingly high efficiency of 11.0-11.3%, even under a preliminary testing. More importantly, based on a low volatility 3-methoxypropionitrile electrolyte and a solvent-free ionic liquid electrolyte, cells have corresponding >9.0% and approximately 7.4% efficiencies retained over 95% of their initial performances after 1000 h full sunlight soaking at 60 degrees C. With the aid of electrical impedance measurements, we further disclose that, compared to the cell with an acetonitrile-based electrolyte, a dye-sensitized solar cell with an ionic liquid electrolyte shows a feature of much shorter effective electron diffusion lengths due to the lower electron diffusion coefficients and shorter electron lifetimes in the mesoporous titania film, explaining the photocurrent difference between these two type devices. This highlights the next necessary efforts to further improve the efficiency of cells with ionic liquid electrolytes, facilitating the large-scale production and application of flexible thin film mesoscopic solar cells.     

Cyclometalated ruthenium complex as a promising sensitizer in dye-sensitized solar cells

Ruthenocycle bis(4,4′-dicarboxy-2,2′-bipyridine)(2-phenylpyridine-²C,N)ruthenium(II) hexafluorophosphate was used as a sensitizer in a dye-sensitized solar cell (DSSC) based on nanocrystalline TiO₂, which was applied onto a conducting substrate. Its electrochemical and spectral characteristics were studied. It was found that, when the DSSC was illuminated with visible light of power 35 mW/cm², the short-circuit current density was 11.6 mA cm^?2 and the open-circuit voltage was 0.49 V. The efficiency (η) of DSSC at a fill factor of 45% was 7.1%. Using the method of modulation spectroscopy of photocurrents and photopotentials, the life time and transit time of electrons were found to be 7 and 5 ms, respectively, and the diffusion coefficient of electrons was found to be 10^?5 cm² s^?1. Comparing the life and transit times of electron, it was concluded that the photogenerated electrons had time to reach the conducting substrate during their life time.     

A high molar extinction coefficient sensitizer for stable dye-sensitized solar cells

An amphiphilic heteroleptic polypyridyl ruthenium complex with a high molar extinction coefficient was synthesized and demonstrated as an efficient, thermostable sensitizer in nanocrystalline dye-sensitized solar cells.     

Electron-rich heteroaromatic conjugated bipyridine based ruthenium sensitizer for efficient dye-sensitized solar cells

A novel heteroleptic ruthenium complex carrying a heteroaromatic-4,4'-pi-conjugated 2,2'-bipyridine [Ru(II)LL'(NCS)(2)] (L = 4,4'-bis[(E)-2-(3,4-ethylenedioxythien-2-yl)vinyl]-2,2'-bipyridine, L' = 4,4'-(dicarboxylic acid)-2,2'-bipyridine) was synthesized and used in dye-sensitized solar cells, yielding photovoltaic efficiencies of 9.1% under standard global AM 1.5 sunlight.     

Facile synthesis of thick ordered mesoporous TiO2 film for dye-sensitized solar cell use

Crack-free thick ordered mesoporous TiO₂ films with excellent optical quality have been synthesized by combination of “Doctor Blade” technique and a two-step evaporation induced self-assembly (EISA) method. By employing the as-synthesized mesoporous film with the thickness of 7 μm as the photoanode in dye-sensitized solar cell (DSC), a solar conversion efficiency of 6.53% has been obtained at 30 mW cm⁻² light intensity.     

A high molar extinction coefficient charge transfer sensitizer and its application in dye-sensitized solar cell

A high molar extinction coefficient charge transfer sensitizer tetrabutylammonium [Ru(4,-carboxylic acid-4′-carboxylate-2,2′-bipyridine)(4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)-2,2′-bipyridine)(NCS)₂], is developed which upon anchoring onto nanocrystalline TiO₂ films exhibit superior power conversion efficiency compared to the standard sensitizer bistetrabutylammonium cis-dithiocyanatobis(4,4′-dicarboxylic acid-2,2′-bipyridine)ruthenium(II) (N719). The new sensitizer anchored TiO₂ films harvest visible light very efficiently over a large spectral range and produce a short-circuit photocurrent density of 18.84 mA/cm², open-circuit voltage 783 mV and fill factor 0.73, resulting remarkable solar-to-electric energy conversion efficiency (η) 10.82, under Air Mass (AM) 1.5 sunlight. The Time Dependent Density Functional Theory (TDDFT) excited state calculations of the new sensitizer show that the first three HOMOs have ruthenium t_2g character with sizable contribution coming from the NCS ligands and the π-bonding orbitals of the 4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)-2,2′-bipyridine. The LUMO is a π^* orbital localized on the 4,4′-dicarboxylic acid-2,2′-bipyridine ligand.     

A highly efficient organic sensitizer for dye-sensitized solar cells

We have synthesized a highly efficient organic dye for a dye-sensitized solar cell; the overall solar-to-energy conversion efficiency was 9.1% at AM 1.5 illumination (100 mW cm(-2)): short-circuit current density (J(sc)) = 18.1 mA cm(-2), open circuit photovoltage (V(oc)) = 743 mV and fill factor (ff) = 0.675.     

Phenomenally high molar extinction coefficient sensitizer with "donor-acceptor" ligands for dye-sensitized solar cell applications

A phenomenally high molar extinction coefficient heteroleptic ruthenium(II) complex [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-(4-{4-methyl-2,5-bis[3-methylbutoxy]styryl}-2,5-bis[3-methylbutoxy]-2,2'-bipyridine)(NCS) 2] ( DCSC13) was synthesized by incorporating donor-acceptor ligands. The absorption spectrum of the DCSC13 sensitizer is dominated by metal-to-ligand charge-transfer transitions (MLCT) in the visible region, with absorption maxima appearing at 442 and 554 nm. The lowest MLCT absorption bands are red-shifted, and the molar extinction coefficients of these bands are significantly higher at 72,100 and 30,600 M(-1) cm(-1), respectively, when compared to those of the analogous [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dimethyl-2,2'-bipyridine)(NCS)2] (N820) sensitizer. The DCSC13 complex, when anchored on nanocrystalline TiO 2 films, exhibited increased short-circuit photocurrent and consequent power-conversion efficiency when compared with the N820 sensitizer.     

Characteristics of high efficiency dye-sensitized solar cells

Impedance spectroscopy was applied to investigate the characteristics of dye-sensitized nanostructured TiO2 solar cells (DSC) with high efficiencies of light to electricity conversion of 11.1% and 10.2%. The different parameters, that is, chemical capacitance, steady-state transport resistance, transient diffusion coefficient, and charge-transfer (recombination) resistance, have been interpreted in a unified and consistent framework, in which an exponential distribution of the localized states in the TiO2 band gap plays a central role. The temperature variation of the chemical diffusion coefficient dependence on the Fermi-level position has been observed consistently with the standard multiple trapping model of electron transport in disordered semiconductors. A Tafel dependence of the recombination resistance dependence on bias potential has been rationalized in terms of the charge transfer from a distribution of surface states using the Marcus model of electron transfer. The current-potential curve of the solar cells has been independently constructed from the impedance parameters, allowing a separate analysis of the contribution of different resistive processes to the overall conversion efficiency.     

Engineering of a novel ruthenium sensitizer and its application in dye-sensitized solar cells for conversion of sunlight into electricity

A novel ligand 4,4'-bis(carboxyvinyl)-2,2'-bipyridine (L) and its ruthenium(II) complex [Ru(II)L(2)(NCS)(2)] (K8) were synthesized and characterized by analytical, spectroscopic, and electrochemical techniques. The performance of the K8 complex as a charge transfer photosensitizer in nanocrystalline TiO(2) based solar cells was studied. When the K8 complex anchored onto a nanocrystalline TiO(2) film, we achieved very efficient sensitization yielding 77 +/-5% incident photon-to-current efficiencies (IPCE) in the visible region using an electrolyte consisting of 0.6 M methyl-N-butyl imidiazolium iodide, 0.05 M iodine, 0.05 M LiI, and 0.5 M 4-tert-butylpyridine in a 50/50 (v/v) mixture of valeronitrile and acetonitrile. Under standard AM 1.5 sunlight, the complex K8 gave a short circuit photocurrent density of 18 +/- 0.5 mA/cm(2), and the open circuit voltage was 640 +/- 50 mV with fill factor of 0.75 +/- 0.05, corresponding to an overall conversion efficiency of 8.64 +/- 0.5%.     

A panchromatic boradiazaindacene (BODIPY) sensitizer for dye-sensitized solar cells

A novel distyryl-substituted boradiazaindacene (BODIPY) dye displays interesting properties as a sensitizer in DSSC systems, opening the way to further exploration of structure-efficiency correlation within this class of dyes.     

A long-term stable Pt counter electrode modified by POM-based multilayer film for high conversion efficiency dye-sensitized solar cells

A long-term stable Pt counter electrode modified by POM-based multilayer film has been fabricated by the electrochemical deposition method, which can markedly increase short-circuit photocurrent, open-circuit voltage and the conversion efficiency when used in dye-sensitized solar cells (DSSCs).     

Evaluation of a ruthenium oxyquinolate architecture for dye-sensitized solar cells

Synthesis of the [Ru(dcbpy)(2)(OQN)](+) complex is reported in which dcbpy and OQN(-) are the bidentate 4,4'-dicarboxy-2,2'-bipyridyl and 8-oxyquinolate ligands, respectively. Spectroscopic, electrochemical, and theoretical analyses are indicative of extensive Ru(OQN) molecular orbital overlap due to degenerate Ru d(π) and OQN p(π) mixing. [Ru(dcbpy)(2)(OQN)](+) displays spectroscopic properties remarkably similar to those of the N3 dye, making it a promising candidate for application in dye-sensitized solar cell devices. However, its solar power conversion efficiency requires further optimization.     

Synthesis of new di-anchoring organic sensitizer based on quinoxaline acceptor for dye-sensitized solar cells

New quinoxaline-based organic sensitizer bearing di-anchoring group for dye-sensitized solar cells (DSSCs) was synthesized from diethyl 4,5-diaminophthaltate, in which was prepared under mild condition by using Takehito’s method. The synthesized sensitizer was compared with mono-anchoring sensitizer through absorption spectra, emission spectra, J-V curve, and IPCE spectra, indicating the di-anchoring group leads to a noticeable improvement of J_sc value owing to more efficient intramolecular charge transfer and channel number increment.     

A dyadic sensitizer for dye solar cells with high energy-transfer efficiency in the device.

A new bichromophoric dyad based on an alkyl-functionalized aminonaphthalimide as energy-donor chromophore and [Ru(dcbpy)2(acac)]Cl (dcbpy=4,4'-dicarboxybipyridine, acac=acetylacetonato) as energy acceptor and sensitizing chromophore is synthesized. Efficient quenching of the donor-chromophore emission is observed in solution, presumably due to resonant energy transfer. This dyad is then used as a sensitizer in a dye solar cell. By comparing the spectral properties of transparent dye solar cells sensitized with the dyad and [Ru(dcbpy)2(acac)]Cl, it is possible to demonstrate that photons absorbed by the donor moiety also contribute significantly to the generation of current. Instead of using acceptor luminescence as a probe, enhanced photocurrent generation is employed to estimate the energy-transfer efficiency. Fitting theoretical to experimental external quantum efficiency functions gives a value for the energy-transfer efficiency of 85 %. Evaluation of the maximum output power of dye solar cells sensitized with the dyad and [Ru(dcbpy)2(acac)]Cl showed, under selective illumination at the absorption maximum of the donor chromophore, that the introduction of the energy-donor moiety leads to a significant increase in the monochromatic maximum output power under blue illumination. This result demonstrates the usefulness of energy transfer for the generation of current in dye-sensitized solar cells.