A single centre water splitting dye complex adsorbed on rutile TiO2(110): photoemission, x-ray absorption, and optical spectroscopy

A single centre water splitting dye complex (aqua(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2':6',6'-terpyridine)Ruthenium(II)), along with a related complex ((2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2':6',6'-terpyridine)chloride Ruthenium(II)), has been investigated using photoemission and compared to molecules with similar structures. Dye molecules were deposited in situ using ultra-high vacuum electrospray deposition, which allows for the deposition of thermally labile molecules, such as these dye molecules. Adsorption of the dye molecules on the rutile TiO(2)(110) surface has been studied using core-level and valence photoemission. Core-level photoemission spectra reveal that each complex bonds to the surface via deprotonation of its carboxylic acid groups. A consideration of the energy level alignments reveals that both complexes are capable of charge transfer from the adsorbed molecules to the conduction band of the rutile TiO(2) substrate.     

Charge transfer dynamics of model charge transfer centers of a multicenter water splitting dye complex on rutile TiO2(110)

Charge transfer dynamics between an adsorbed molecule and a rutile TiO(2)(110) surface have been investigated in three organometallic dyes related to multicenter water splitting dye complexes: Ru 535 (cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)), Ru 455 (cis-bis(2,2'-bipyridyl)-(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)), and Ru 470 (tris(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)). The adsorption of the dye molecules on the rutile TiO(2)(110) surface has been studied using core-level and valence photoemission. Dye molecules were deposited in situ using ultrahigh vacuum electrospray deposition. Core-level photoemission spectra reveal that each complex bonds to the surface via deprotonation of two carboxylic groups. All three dye complexes show evidence of ultrafast charge transfer to the TiO(2) substrate using the core-hole clock implementation of resonant photoemission spectroscopy.     

Engineering of efficient panchromatic sensitizers for nanocrystalline TiO(2)-based solar cells.

A new series of panchromatic ruthenium(II) sensitizers derived from carboxylated terpyridyl complexes of tris-thiocyanato Ru(II) have been developed. Black dye containing different degrees of protonation [(C(2)H(5))(3)NH][Ru(H(3)tcterpy)(NCS)(3)] 1, [(C(4)H(9))(4)N](2)[Ru(H(2)tcterpy)(NCS)(3)] 2, [(C(4)H(9))(4)N](3)[Ru(Htcterpy)(NCS)(3)] 3, and [(C(4)H(9))(4)N](4)[Ru(tcterpy)(NCS)(3)] 4 (tcterpy = 4,4',4' '-tricarboxy-2,2':6',2' '-terpyridine) have been synthesized and fully characterized by UV-vis, emission, IR, Raman, NMR, cyclic voltammetry, and X-ray diffraction studies. The crystal structure of complex 2 confirms the presence of a Ru(II)N6 central core derived from the terpyridine ligand and three N-bonded thiocyanates. Intermolecular H-bonding between carboxylates on neighboring terpyridines gives rise to 2-D H-bonded arrays. The absorption and emission maxima of the black dye show a bathochromic shift with decreasing pH and exhibit pH-dependent excited-state lifetimes. The red-shift of the emission maxima is due to better pi-acceptor properties of the acid form that lowers the energy of the CT excited state. The low-energy metal-to-ligand charge-transfer absorption band showed marked solvatochromism due to the presence of thiocyanate ligands. The Ru(II)/(III) oxidation potential of the black dye and the ligand-based reduction potential shifted cathodically with decreasing number of protons and showed more reversible character. The adsorption of complex 3 from methoxyacetonitrile solution onto transparent TiO(2) films was interpreted by a Langmuir isotherm yielding an adsorption equilibrium constant, K(ads), of (1.0 +/- 0.3) x 10(5) M(-1). The amount of dye adsorbed at monolayer saturation was (n(alpha) = 6.9 +/- 0.3) x 10(-)(8) mol/mg of TiO(2), which is around 30% less than that of the cis-di(thiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) complex. The black dye, when anchored to nanocrystalline TiO(2) films achieves very efficient sensitization over the whole visible range extending into the near-IR region up to 920 nm, yielding over 80% incident photon-to-current efficiencies (IPCE). Solar cells containing the black dye were subjected to analysis by a photovoltaic calibration laboratory (NREL, U.S.A.) to determine their solar-to-electric conversion efficiency under standard AM 1.5 sunlight. A short circuit photocurrent density obtained was 20.5 mA/cm(2), and the open circuit voltage was 0.72 V corresponding to an overall conversion efficiency of 10.4%.     

Electronic and molecular surface structure of Ru(tcterpy)(NCS)3 and Ru(dcbpy)2(NCS)2 adsorbed from solution onto nanostructured TiO2: a photoelectron spectroscopy study

The element specificity of photoelectron spectroscopy (PES) has been used to compare the electronic and molecular structure of the dyes Ru(tcterpy)(NCS)3 (BD) and Ru(dcbpy)2(NCS)2 adsorbed from solution onto nanostructured TiO2. Ru(dcbpy)2(NCS)2 was investigated in its acid (N3) and in its 2-fold deprotonated form (N719) having tetrabutylammonium (TBA+) as counterions. A comparison of the O1s spectra for the dyes indicates that the interactions through the carboxylate groups with the TiO2 surface are very similar for the dyes. However, we observe that some of the dye molecules also interact through the NCS groups when adsorbed at the TiO2 surface. Comparing the N719 and the N3 molecule, the fraction of NCS groups interacting through the sulfur atoms is smaller for N719 than for N3. We also note that the counterion TBA+ is coadsorbed with the N719 and BD molecules although the amount was smaller than expected from the molecular formulas. Comparing the valence levels for the dyes adsorbed on TiO2, the position of the highest occupied electronic energy level is similar for N3 and N719, while that for BD is lower by 0.25 eV relative to that of the other complexes.     

NC-AFM observation of atomic scale structure of rutile-type TiO2(110) surface prepared by wet chemical process

We succeeded in observing the atomic scale structure of a rutile-type TiO2(110) single-crystal surface prepared by the wet chemical method of chemical etching in an acid solution and surface annealing in air. Ultrahigh vacuum noncontact atomic force microscopy (UHV-NC-AFM) was used for observing the atomic scale structures of the surface. The UHV-NC-AFM measurements at 450 K, which is above a desorption temperature of molecularly adsorbed water on the TiO2(110) surface, enabled us to observe the atomic scale structure of the TiO2(110) surface prepared by the wet chemical method. In the UHV-NC-AFM measurements at room temperature (RT), however, the atomic scale structure of the TiO2(110) surface was not observed. The TiO2(110) surface may be covered with molecularly adsorbed water after the surface was prepared by the wet chemical method. The structure of the TiO2(110) surface that was prepared by the wet chemical method was consistent with the (1 x 1) bulk-terminated model of the TiO2(110) surface.     

Preillumination of TiO2 and Ta2O5 photoactive thin films as a tool to tailor the synthesis of composite materials

Illumination of TiO 2 thin films with UV light is known to induce the transformation of the surface of this material from partially hydrophobic into fully hydrophilic. The present work shows that this transformation is accompanied by other effects that may be used to control the synthesis of composite materials. For this purpose, TiO 2 and Ta 2O 5 transparent thin films with a columnar structure and open pores were prepared by electron evaporation at glancing angles. Transparent TiO 2 thin films with micropores (i.e., pores smaller than 2 nm) prepared by plasma enhanced chemical vapor deposition (PECVD) were also used. All these films became hydrophilic upon UV illumination. Rhodamine 6G and Rhodamine 800 dyes were irreversibly adsorbed within the columns of the TiO 2 and Ta 2O 5 thin films by immersion into a water solution of these molecules. Isolated and aggregated molecules of these two dyes were detected by visible absorption spectroscopy. The infiltration adsorption efficiency was directly correlated with the acidity of the medium, increasing at basic pHs as expected from simple considerations based on the concepts of the point of zero charge (PZC) in colloidal oxides. The infiltration experiments were repeated with columnar TiO 2 and Ta 2O 5 thin films that were subjected to preillumination with UV light. It was found that this treatment produced a modification in the type (isolated or aggregated) and amount of dye molecules incorporated into the pores. Moreover, the selective adsorption of a given dye in preilluminated areas of the films permitted the lithographic coloring of the films. Preillumination also controls the UV induced deposition of silver on the surface of the microporous TiO 2 thin films. It was found that the size distribution of the formed silver nanoparticles was dependent on the preillumination treatment and that a well-resolved surface plasmon resonance at around 500 nm was only monitored in the preilluminated films. A model is proposed to account for the effects induced by UV preillumination on the TiO 2 and Ta 2O 5 oxide surfaces. The possibilities of this type of light treatment for the tailored synthesis of nanocomposite thin films (i.e., dye-oxide, metal nanoparticles-oxide) are highlighted.     

Effect of additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells

The effects of deoxycholic acid (DCA) and 4-tert-butylpyridine (TBP) as additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells were investigated. DCA coadsorption improved both the photocurrent and photovoltage of the solar cells, even though it decreased the amount of dye adsorbed on the TiO2 electrode. The improved photocurrent may arise from suppression of the deactivation of the excited state via quenching processes between dye molecules or a more negative LUMO level of the dye in the presence of DCA, resulting in a high electron-injection yield from the dye into TiO2. The increased photovoltage is probably due to suppression of recombination between the injected electrons and I3- ions on the TiO2 surface (dark current). The addition of TBP to the electrolyte also markedly improved the photovoltage and fill factor of the solar cell, and consequently, the total conversion efficiency increased from 3.6% to 7.5%. FT-IR spectroscopy indicated that a large amount of TBP was adsorbed on the dye-coated TiO2 films in the presence of Li cations. This result suggests that TBP, like DCA, suppressed the dark current on the TiO2 surface, which resulted in the improved photovoltage.     

Spectroelectrochemical studies of hole percolation on functionalised nanocrystalline TiO2 films: a comparison of two different ruthenium complexes

We report the application of spectroelectrochemical techniques to compare the hole percolation dynamics of molecular networks of two ruthenium bipyridyl complexes adsorbed onto mesoporous, nanocrystalline TiO(2) films. The percolation dynamics of the ruthenium complex cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-tridecyl) ruthenium(II), N621, is compared with those observed for an analogous dye with an additional tri-phenyl amine (TPA) donor moiety, cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-bis(vinyltriphenylamine)) ruthenium(II), HW456. The in situ oxidation of these ruthenium complexes adsorbed to the TiO(2) films is monitored by cyclic voltammetry and voltabsorptometry, whilst the dynamics of hole (cation) percolation between adsorbed ruthenium complexes is monitored by potentiometric spectroelectrochemistry and chronoabsorptometry. The hole diffusion coefficient, D(eff), is shown to be dependent on the dye loading on the nanocrystalline TiO(2) film, with a threshold observed at ～60% monolayer surface coverage for both dyes. The hole diffusion coefficient of HW456 is estimated to be 2.6 × 10(-8) cm(2)/s, 20-fold higher than that obtained for the control N621, attributed to stronger electronic coupling between the TPA moieties of HW456 accelerating the hole percolation dynamics. The presence of mercuric ions, previously shown to bind to the thiocyanates of analogous ruthenium complexes, resulted in a quenching of the hole percolation for N621/TiO(2) films and an enhancement for HW456/TiO(2) films. These results strongly suggest that the hole percolation pathway is along the overlapped neighbouring -NCS groups for the N621 molecules, whereas in HW456 molecules cation percolation proceeds between intermolecular TPA ligands. These results are discussed in the context of their relevance to the process of dye regeneration in dye sensitised solar cells, and to the molecular wiring of wide bandgap inorganic materials for battery and sensing applications.     

The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO2(110) in CO oxidation reaction

This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ～1.5 nm and two-atomic layer height corresponding to ～50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.     

Characterization of the adsorption of Ru-bpy dyes on mesoporous TiO2 films with UV-Vis, Raman, and FTIR spectroscopies

In the present work the adsorption of a new dye, [Ru(dcbpyH(2))(2)(bpy-TPA(2))](PF(6))(2), and the well-known (Bu(4)N)(2)[Ru(dcbpyH)(2)(NCS)(2)] complex on mesoporous anatase films were investigated to clarify the role of the carboxylate groups in the anchoring process of the dyes on the semiconductor surface. For this purpose UV-vis, Raman, resonance Raman, and ATR-FTIR spectroscopies have been used. The results of the Raman experiments at different excitation wavelengths demonstrate that photoinduced charge-transfer processes take place efficiently between the adsorbate and the substrate. Moreover, this is the first time that the Raman spectrum of a Ru-bpy dye (in this case, the dye N719) adsorbed on TiO(2) has been obtained without the resonance condition, only by means of SERS enhancement. The coordination of both complexes on the TiO(2) paste films is proposed to occur via bidentate or bridging linkage.     

STM observation of a ruthenium dye adsorbed on a TiO2(110) surface

Individual Ru(4,4'-dicarboxy-2,2'-bipyridine)2(NCS)2 molecules, commonly known as N3, adsorbed on a TiO2 surface were visualized with a scanning tunneling microscope (STM) operated in ultrahigh vacuum. A TiO2(110)-(1 x 1) crystal was taken out from the vacuum vessel and immersed into an acetonitrile solution of N3. A monolayer of pivalate ((CH3)3CCOO-) ions was used to protect the (1 x 1) surface from contamination during the wetting process of the N3 adsorption. The N3 molecules adsorbed on the flat terraces protruded by 0.65 nm from the pivalate monolayer. The image height difference of the admolecules could be understood with the assumption that the N3 molecules anchor to the TiO2 surface via two carboxyl groups. The number density of the N3 molecules on the steps was higher than that on the terraces. The poorly coordinated Ti atoms exposed at the step edges form preferential sites where the carboxyl groups can approach, due to a lower steric obstacle or because the structure of the adsorbed N3 molecules suffers less distortion.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

Directed adhesion and patterning by ultraviolet irradiation of TiO2(110)

Forces of adhesion between a hydroxylated silicon oxide tip and a TiO(2)(110) surface, before and after irradiation of the surface with 254 nm light, were measured using atomic force microscopy. The work of adhesion before and after irradiation was 32 and 166 mJ/m(2), respectively, but a difference was observed only if ultraviolet light exposure was used in the presence of oxygen. The change in adhesion correlated strongly with decreasing water contact angle, which changed from ca. 70 to 0° because of irradiation. The contrast in adhesion between irradiated and nonirradiated regions of the surface makes possible a simple method of patterning molecules with micrometer, and potentially nanoscale, resolution. As an example, fluorescein was selectively adsorbed onto hydrophilic regions of the surface by spin coating an ethanolic fluorescein solution onto TiO(2)(110) that had been irradiated through a photomask.     

Significant efficiency improvement of the black dye-sensitized solar cell through protonation of TiO2 films

This paper describes the influence of acid pretreatment ofTiO2 mesoporous films prior to dye sensitization on the performance of dye-sensitized solar cells based on [(C4H9)4N]3[Ru(Htcterpy)(NCS)3] (tcterpy = 4,4',4"-tricarboxy- 2,2',2"-terpyridine), the so-called black dye. The HCl pretreatment caused an increase in overall efficiency by 8%, with a major contribution from photocurrent improvement. It is speculated, from the analysis of incident photon-to-electron conversion efficiency, UV-vis absorption spectra, redox properties of the dye and TiO2, and the impedance spectra of the dye-sensitized solar cells, that photocurrent enhancement is attributed to the increases in electron injection and/or charge collection efficiency besides the improvement of light harvesting efficiency upon HCl pretreatment. Open-circuit photovoltage (V(oc)) remained almost unchanged in the case of significant positive shift of flat band potential for TiO2 upon HCl pretreatment. The suppression of electron transfer from conduction band electrons to the I3- ions in the electrolyte upon HCl pretreatment, reflected by the increased resistance at the TiO2/dye/electrolyte interface and reduced dark current, resulted in a V(oc) gain, which compensated the V(oc) loss due to the positive shift of the flat band. Using the HCl pretreatment approach, 10.5% of overall efficiency with the black dye was obtained under illumination of simulated AM 1.5 solar light (100 mW cm(-2)) using an antireflection film on the cell surface.     

Photocatalytic reactivities of Nafion-coated TiO2 for the degradation of charged organic compounds under UV or visible light

Nafion (perfluorinated polymer with sulfonate groups)-coated TiO2 particles (Nf/TiO2) were prepared and their reactivities for the photocatalytic degradation (PCD) of charged organic substrates were investigated. The presence of Nafion adlayers drastically changed the positive TiO2 surface charge to a negative one over the entire pH range and significantly influenced the PCD kinetics and mechanisms. The UV-induced PCD of tetramethylammonium (TMA; cationic substrate) was greatly enhanced in the presence of Nafion adlayers on TiO2 because the ion-exchange sites within the Nafion can hold cationic substrates. On the other hand, despite the unfavorable electrostatic interaction between the Nf/TiO2 and anionic substrates, the PCD of dichloroacetate (DCA) and acid orange 7 (AO7) with Nf/TiO2 was not significantly inhibited. The visible-light-sensitized degradation of dyes was enhanced with Nf/TiO2 not only for cationic dyes (methylene blue (MB) and rhodamine B (RhB)) whose uptake on Nf/TiO2 is enhanced, but also for an anionic dye (AO7) that is less adsorbed on Nf/TiO2. The unexpected behavior in AO7 degradation seems to be related to the role of the Nafion layer in retarding the charge recombination. These observations indicate that Nf/TiO2 can enhance the PCD reactivity for cationic substrates without sacrificing the PCD reactivity for anionic substrates. In addition, it was found that the sensitized degradation of RhB followed a different path when the surface of TiO2 was coated with Nafion. The N-de-ethylation of RhB that leads to the generation of rhodamine-110 was a prevailing path with Nf/TiO2, whereas the cleavage of the chromophoric ring structure was dominant with pure TiO2. The effects of Nafion adlayers on the photoinduced electron transfer and PCD kinetics and mechanisms are discussed.     

Light-induced rearrangements of chemisorbed dyes on anatase(101)

Photoinduced molecular rearrangements are important in daily events essential for life such as visual perception and photo-protection of light harvesting complexes in plants. In this study we demonstrate that similar photoarrangements appear in an analogous technological application where the device performance is controlled by chromophores in sensitized anatase TiO(2), one of the main components for light-harvesting in dye-sensitized solar cells (DSC). STM reveals that illumination leads to distortions of organic dyes containing conjugated backbones and of cis-bis(isothiocyanate)-bis-(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II)-bis(tetrabutylammonium), known as N719. The dyes were adsorbed in a closed-packed mode on an anatase(101) single crystal surface and imaged in the dark and under white light illumination in an ultra-high vacuum (UHV). STM images of N719 clearly suggest rearrangements caused by rotation of the dye. Conversely, organic dyes rearrange by photoisomerization depending on the number of double bonds, their position in the molecular structure and on the ligand modifications.     

First direct visualization of spillover species emitted from pt nanoparticles

We studied the methanol adsorption behavior of Pt nanoparticles that were vacuum-deposited on a TiO(2)(110) surface at room temperature by using an ultrahigh vacuum (UHV) scanning tunneling microscope (STM). A large number of bright spots were observed on fivefold-coordinated Ti (Ti(5c)) rows of the TiO(2)(110) surface after exposure of the Pt/TiO(2)(110) to methanol vapor. We assigned the bright spots to methoxy species. These were mobile and were found to hop along the Ti(5c) rows. In situ time-resolved STM observations of the formation and migration of the bright spots on the Pt/TiO(2)(110) were carried out in the presence of methanol. The bright spots were produced at the periphery of the Pt nanoparticles and migrated to the substrate Ti(5c) rows. We discuss the spillover process and behavior of the methoxy species on the Pt/TiO(2)(110).     

The mechanism of the water-gas shift reaction on Cu/TiO2(110) elucidated from application of density-functional theory

The Cu/TiO(2)(110) surface displays a great catalytic activity toward the water-gas shift reaction (WGSR), for which Cu is considered to be the most active metal on a TiO(2)(110)-supported surface. Experiments revealed that Cu nanoparticles bind preferentially to the terrace and steps of the TiO(2)(110) surface, which would not only affect the growth mode of the surface cluster but also enhance the catalytic activity, unlike Au nanoparticles for which occupancy of surface vacancies is favored, resulting in poorer catalytic performance than Cu. With density-functional theory we calculated some possible potential-energy surfaces for the carboxyl and redox mechanisms of the WGSR at the interface between the Cu cluster and the TiO(2) support. Our results show that the redox mechanism would be the dominant path; the resident Cu clusters greatly diminish the barrier for CO oxidation (22.49 and 108.68 kJ mol(-1), with and without Cu clusters, respectively). When adsorbed CO is catalytically oxidized by the bridging oxygen of the Cu/TiO(2)(110) surface to form CO(2), the release of CO(2) from the surface would result in the formation of an oxygen vacancy on the surface to facilitate the ensuing water splitting (barrier 34.90 vs. 50.49 kJ mol(-1), with and without the aid of a surface vacancy).     

Photophysical and (photo)electrochemical properties of a coumarin dye

A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.     

Effects of tethering alkyl chains for amphiphilic ruthenium complex dyes on their adsorption to titanium oxide and photovoltaic properties

Ruthenium (II) complex dye, Ru(4,4'-dicarboxyl-2,2'-bipyridine)(4-nonyl-2,2'-bipyridine) (NCS)(2), (denoted as RuC9) tethering single alkyl chain was synthesized and well characterized. Its adsorption behavior onto the mesoporous TiO(2) and photovoltaic properties were compared with Z907 which has similar chemical structure but tethers two alkyl chains. RuC9 dyes tend to aggregate into vesicles in the acetonitrile/t-butanol co-solvent as a result of the amphiphilic structure, whereas Z907 dyes aggregate into lamellae. The dye-sensitized solar cell (DSSC) with RuC9 dye showed higher short-circuit photocurrent than that with Z907, attributing to its higher molar optical extinction coefficient and more adsorption amount onto the mesoporous TiO(2). However, the DSSC with Z907 dye has higher open-circuit photovoltage and power conversion efficiency, presumably due to the fact that Z907 with more alkyl chains formed a molecular layer with higher hydrophobicity. It reduced the charge recombination in the interface between the dye-sensitized mesoporous TiO(2) and electrolyte as verified by the electrochemical impedance spectroscopy and intensity modulated photocurrent and photovoltage spectroscopies.