Effect of Substituents in Catechol Dye Sensitizers on Photovoltaic Performance of Type II Dye‐Sensitized Solar Cells

In order to provide a direction in molecular design of catechol (Cat) dyes for type II dye‐sensitized solar cells (DSSCs), the dye‐to‐TiO₂ charge‐transfer (DTCT) characteristics of Cat dyes with various substituents and their photovoltaic performance in DSSCs are investigated. The Cat dyes with electron‐donating or moderately electron‐withdrawing substituents exhibit a broad absorption band corresponding to DTCT upon binding to TiO₂ films, whereas those with strongly electron‐withdrawing substituents exhibit weak DTCT. This study indicates that the introduction of a moderately electron‐withdrawing substituent on the Cat moiety leads to not only an increase in the DTCT efficiency, but also the retardation of back electron transfer. This results in favorable conditions for the type II electron‐injection pathway from the ground state of the Cat dye to the conduction band of the TiO₂ electrode by the photoexcitation of DTCT bands.     

Oligothiophene-containing coumarin dyes for efficient dye-sensitized solar cells

We have developed oligothiophene-containing coumarin dyes fully functionalized for dye-sensitized nanocrystalline TiO(2) solar cells (DSSCs). DSSCs based on the dyes gave good performance in terms of incident photon-to-current conversion efficiency (IPCE) in the range of 400-800 nm. A solar energy-to-electricity conversion efficiency (eta) of 7.4% was obtained with a DSSC based on 2-cyano-3-[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)-[2,2']bithiophenyl-5-yl]acrylic acid (NKX-2677) under simulated AM 1.5G irradiation (100 mW cm(-2)) with a mask: short-circuit current density (J(sc)) = 13.5 mA cm(-2); open-circuit voltage (V(oc)) = 0.71 V; fill factor (FF) = 0.77. Transient absorption spectroscopy measurements indicated that electron injection from NKX-2677 to the conduction band of TiO(2) is very rapid (<100 fs), which is much faster than the emission lifetime of the dye (1.0 ns), giving a highly efficient electron injection yield of near unity.     

Influence of surface-attachment functionality on the aggregation, persistence, and electron-transfer reactivity of chalcogenorhodamine dyes on TiO2

Chalcogenorhodamine dyes bearing phosphonic acids and carboxylic acids were compared as sensitizers of nanocrystalline TiO(2) in dye-sensitized solar cells (DSSCs). The dyes were constructed around a 3,6-bis(dimethylamino)chalcogenoxanthylium core and varied in the 9 substituent: 5-carboxythien-2-yl in dyes 1-E (E = O, Se), 4-carboxyphenyl in dyes 2-E (E = O, S), 5-phosphonothien-2-yl in dyes 3-E (E = O, Se), and 4-phosphonophenyl in dyes 4-E (E = O, Se). All dyes adsorbed to TiO(2) as mixtures of H aggregates and monomers, which exhibited broadened absorption spectra relative to those of purely amorphous monolayers. Surface coverages of dyes and the extent of H aggregation varied minimally with the surface-attachment functionality, the structure of the 9-aryl group, and the identity of the chalcogen heteroatom. Carboxylic acid-functionalized dyes 1-E and 2-E desorbed rapidly and completely from TiO(2) into acidified CH(3)CN, but phosphonic acid-functionalized dyes 3-E and 4-E persisted on TiO(2) for days. Short-circuit photocurrent action spectra of DSSCs corresponded closely to the absorptance spectra of dye-functionalized films; thus, H aggregation did not decrease the electron-injection yield or charge-collection efficiency. Maximum monochromatic incident photon-to-current efficiencies (IPCEs) of DSSCs ranged from 53 to 95% and were slightly higher for carboxylic acid-functionalized dyes 1-E and 2-E. Power-conversion efficiencies of DSSCs under white-light illumination were low (<1%), suggesting that dye regeneration was inefficient at high light intensities. The photoelectrochemical performance (under monochromatic or white-light illumination) of 1-E and 2-E decayed significantly within 20-80 min of the assembly of DSSCs, primarily because of the desorption of the dyes. In contrast, the performance of phosphonic acid-functionalized dyes remained stable or improved slightly on similar timescales. Thus, replacing carboxylic acids with phosphonic acids increased the inertness of chalcogenorhodamine-TiO(2) interfaces without greatly impacting the aggregation of dyes or the interfacial electron-transfer reactivity.     

Alkyl-functionalized organic dyes for efficient molecular photovoltaics

We designed and synthesized new alkyl-functionalized organic dyes, MK-1 and MK-2, for dye-sensitized solar cells (DSSCs). Based on the MK-2 dye, a high performance of efficiency (eta, 7.7%; short-circuit current density Jsc = 14.0 mA cm-2, open-circuit voltage Voc = 0.74 V, and fill factor FF = 0.74) was achieved under AM 1.5 G irradiation (100 mW cm-2). Remarkably, the relatively higher Voc for DSSCs based on MK-1 and MK-2 dyes, which have long alkyl chains, were observed among the organic dyes caused by the increasing of the electron lifetime in the conduction band of TiO2. Our molecular design of alkyl-functionalized dyes strongly suggests the promising performance of molecular photovoltaics based on organic dyes.     

Nanocrystalline electrodes based on nanoporous-walled WO3 nanotubes for organic-dye-sensitized solar cells

Nanoporous-walled tungsten oxide (WO(3)) nanotubes (NTs), which had a more positive conduction band edge level compared to that of TiO(2), were applied to various organic dyes for dye-sensitized solar cells (DSSCs). The dye-sensitized WO(3) NTs displayed photosensitization for the organic dyes whose lowest unoccupied molecular orbital (LUMO) level was relatively positive to the conventional TiO(2) electrode and, thus, not applicable for electron injection to the TiO(2) electrode. Electron transport time and electron lifetime for the WO(3) electrode in the DSSCs were investigated. In comparison to the DSSCs based on TiO(2), SnO(2), and In(2)O(3), the WO(3) DSSCs displayed the longest lifetime. On the other hand, non-diffusion-like electron transport may be an issue to apply WO(3) for the DSSCs.     

Kinetics of electron recombination of dye-sensitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO(2) films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dyes N719, C218 and D205, respectively, have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τ(n), of the different dye based NR-DSSCs shows the sequence of C218 > D205 > N719. The higher V(oc) with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO(2) film. In addition, in comparison to the DSSCs with the conventional nanocrystalline particles based TiO(2) films, the NR-DSSCs have shown over two orders of magnitude higher τ(n) when employing N719 as the sensitizer. Nevertheless, the τ(n) of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.     

Surface-treated TiO2 nanoparticles for dye-sensitized solar cells with remarkably enhanced performance

Dye-sensitized solar cells (DSSCs) were prepared by capitalizing on mesoporous P-25 TiO(2) nanoparticle film sensitized with N719 dyes. Subjecting TiO(2) nanoparticle films to TiCl(4) treatment, the device performance was improved. More importantly, O(2) plasma processing of TiO(2) film that was not previously TiCl(4)-treated resulted in a lower efficiency; by contrast, subsequent O(2) plasma exposure after TiCl(4) treatment markedly enhanced the power conversion efficiency, PCE, of DSSCs. Remarkably, with TiCl(4) and O(2) plasma treatments dye-sensitized TiO(2) nanoparticle solar cells produced with 21 μm thick TiO(2) film illuminated under 100 mW/cm(2) exhibited a PCE as high as 8.35%, twice of untreated cells of 3.86%.     

Theoretical investigation of triphenylamine dye/titanium dioxide interface for dye-sensitized solar cells

The structural, electronic and optical features of two metal-free triphenylamine (TPA) organic dyes (namely C206 and C217) before and after binding to a TiO(2) anatase nanoparticle have been investigated in detail, as a model for the corresponding dye-sensitized solar cells (DSSCs). The combination of density functional tight-binding (DFTB), density functional theory (DFT), and time-dependent DFT (TDDFT) approaches are employed. To understand the effects of the linker part in the TPA organic dyes on the energy conversion efficiency of the DSSCs, C217 and C206, which share the same donor and anchor parts but different linker parts, are theoretically evaluated. Our results show that compared with C206 containing just one thienothiophene unit as the linker, for C217 the introduction of one electron-rich 3,4-ethylenedioxythiophene group to the linker part results in stronger couplings with the TiO(2) conduction band and more efficient electron transfer. This difference contributes to the higher efficiency of C217 in DSSCs experiments. This study is expected to assist the molecular design of new and more efficient TPA-based organic dyes for the optimization of the DSSCs.     

基于铝离子掺杂二氧化钛薄膜的染料敏化太阳能电池的光电性能

采用水热法制备出Al3+掺杂二氧化钛薄膜,通过玻璃棒涂于导电玻璃上,在450°C的温度下烧结并将其用N3染料敏化制成染料敏化太阳能电池(DSSCs).通过X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电镜(SEM)及DSSCs测试系统对其进行了测试表征,研究了Al3+掺杂对TiO2晶型及染料敏化太阳能电池的光电性能影响.XPS数据显示Al3+成功掺杂到了TiO2晶格内,由于Al3+的存在,对半导体内电子和空穴的捕获及阻止电子/空穴对的复合发挥重要作用.莫特-肖特基曲线显示掺杂Al3+后二氧化钛平带电位发生正移,并导致电子从染料注入到TiO2的驱动力提高.DSSCs系统测试结果表明,Al3+掺杂的TiO2薄膜光电效率达到6.48%,相对于无掺杂的纯二氧化钛薄膜光电效率(5.58%),其光电效率提高了16.1%,短路光电流密度从16.5mA·cm-2提高到18.2mA·cm-2.     

Charge transport versus recombination in dye-sensitized solar cells employing nanocrystalline TiO2 and SnO2 films

We report a comparison of charge transport and recombination dynamics in dye-sensitized solar cells (DSSCs) employing nanocrystalline TiO(2) and SnO(2) films and address the impact of these dynamics upon photovoltaic device efficiency. Transient photovoltage studies of electron transport in the metal oxide film are correlated with transient absorption studies of electron recombination with both oxidized sensitizer dyes and the redox couple. For all three processes, the dynamics are observed to be 2-3 orders of magnitude faster for the SnO(2) electrode. The origins of these faster dynamics are addressed by studies correlating the electron recombination dynamics to dye cations with chronoamperometric studies of film electron density. These studies indicate that the faster recombination dynamics for the SnO(2) electrodes result both from a 100-fold higher electron diffusion constant at matched electron densities, consistent with a lower trap density for this metal oxide relative to TiO(2), and from a 300 mV positive shift of the SnO(2) conduction band/trap states density of states relative to TiO(2). The faster recombination to the redox couple results in an increased dark current for DSSCs employing SnO(2) films, limiting the device open-circuit voltage. The faster recombination dynamics to the dye cation result in a significant reduction in the efficiency of regeneration of the dye ground state by the redox couple, as confirmed by transient absorption studies of this reaction, and in a loss of device short-circuit current and fill factor. The importance of this loss pathway was confirmed by nonideal diode equation analyses of device current-voltage data. The addition of MgO blocking layers is shown to be effective at reducing recombination losses to the redox electrolyte but is found to be unable to retard recombination dynamics to the dye cation sufficiently to allow efficient dye regeneration without resulting in concomitant losses of electron injection efficiency. We conclude that such a large acceleration of electron dynamics within the metal oxide films of DSSCs may in general be detrimental to device efficiency due to the limited rate of dye regeneration by the redox couple and discuss the implications of this conclusion for strategies to optimize device performance.     

Noncovalent interactions in human plasma proteins analyzed by the comparison of nondenaturing and denaturing micro-2-D gel electrophoresis patterns after polypeptide assignment using matrix-assisted laser desorption/ionization-mass spectrometry and peptide mass fingerprinting

Previously, we reported the analysis of human plasma proteins by 2-DE under nondenaturing conditions (Type-I 2-DE) followed by the assignment of stained spots using MALDI-MS and PMF [1]. Here, we employ 2-DE conditions modified only in the second-dimensional separation; SDS was added in the gradient slab gel aiming to dissociate noncovalently bound proteins/polypeptides (Type-II 2-DE). Totally 169 CBB-stained spots on a micro-2-DE gel were numbered and subjected to polypeptide assignment using MALDI-MS-PMF. One hundred sixty spots out of the 169 provided significant match (p <0.05) with polypeptides in databases. Comparisons of the results of polypeptide assignment on the two 2-DE patterns indicated that 10 polypeptides in 20 stained spots on the Type-I 2-DE pattern [1] shifted toward low-molecular-weight positions on the Type-II 2-DE pattern, demonstrating the presence of noncovalent interactions. Seventeen polypeptides in 38 stained spots were only assigned on the Type-II 2-DE gel, which could mostly be accounted for by the disruption of noncovalent protein-protein interactions in the presence of SDS, i.e., protein/polypeptide complexes which might form smear bands on the Type-I 2-DE gel dissociate to form clear spots on the Type-II 2-DE gel. The method employed here, comparisons of nondenaturing and denaturing 2-DE maps with polypeptide assignment by MALDI-MS-PMF, would enable the simultaneous detection of multiple noncovalent interactions in complex protein/polypeptide systems.     

Zirconium((IV)) and Hafnium((IV)) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO(2) via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)(2) and (TPP)Zr(OAc)(2), and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)(2) and (Pc)Zr(OAc)(2), were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO(2) semiconductor nanoparticles, as well as a good band gap match with I(3) (-)/I(-) pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO(2) nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture.     

Light-induced charge separation in anatase TiO2 particles

Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2).     

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%.     

A novel photoanode architecture of dye-sensitized solar cells based on TiO2 hollow sphere/nanorod array double-layer film

A novel TiO(2) double-layer (DL) film consisting of TiO(2) hollow spheres (HSs) as overlayer and single-crystalline TiO(2) nanorod arrays (RAs) as underlayer was designed as the photoanode of dye-sensitized solar cells (DSSCs). This new-typed TiO(2) HS/RA DL film could significantly improve the efficiency of DSSCs owing to its synergic effects, i.e. the relatively large specific surface area of TiO(2) HSs for effective dye adsorption, enhanced light harvesting capability originated from TiO(2) RA film, and rapid interfacial electron transport in one-dimensional TiO(2) nanorod arrays. The overall energy-conversion efficiency of 4.57% was achieved by the formation of TiO(2) DL film, which is 16% higher than that formed by TiO(2) HS film and far larger than that formed by TiO(2) RA film (η=0.99%). The light absorption and interfacial electron transport, which play important roles in the efficiency of DSSCs, were investigated by UV-vis absorption spectra and electrochemical impedance spectra.     

Change of adsorption modes of dyes on fluorinated TiO2 and its effect on photocatalytic degradation of dyes under visible irradiation

Surface-fluorinated TiO2 (F-TiO2) particles were prepared via the HF etching method. The surface characteristics of fluorinated TiO2, the adsorption modes of dyes, and the reaction pathways for the photocatalytic degradation of dye pollutants under visible light irradiation were investigated. It was found that, in the treatment of TiO2 by HF etching, F(-) not only displaces surface HO(-) but also substitutes some surface lattice oxygen. Using zwitterionic Rhodamine B (RhB) dye as a model, the change of the adsorption mode of RhB on F-TiO2 relative to that on pure TiO2 was validated by adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and IR techniques for the first time. RhB preferentially anchors on pure TiO2 through the carboxylic (-COOH) group, while its adsorption group is switched to the cationic moiety (-NEt 2 group) on F-TiO2. Both the photocatalytic degradation kinetics and mechanisms were drastically changed after surface fluorination. Dyes with positively charged nitrogen-alkyl groups such as methylene blue (MB), malachite green (MG), Rhodamine 6G (Rh6G), and RhB all underwent a rapid N-dealkylation process on F-TiO2, while on pure TiO2 direct cleavage of dye chromophore ring structures predominated. The relationship between surface fluorination and the degradation rate/pathway of dyes under visible irradiation was also discussed in terms of the effect of fluorination on the surface adsorption of dyes and on the energy band structure of TiO2.     

Photosensitization of nanoparticulate TiO2 using a Re(I)-polypyridyl complex: studies on interfacial electron transfer in the ultrafast time domain

We have synthesized a new photoactive rhenium(i)-complex having a pendant catechol functionality [Re(CO)(3)Cl(L)] (1) (L is 4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) for studying the dynamics of the interfacial electron transfer between nanoparticulate TiO(2) and the photoexcited states of this Re(i)-complex using femtosecond transient absorption spectroscopy. Our steady state absorption studies revealed that complex 1 can bind strongly to TiO(2) surfaces through the catechol functionality with the formation of a charge transfer (CT) complex, which has been confirmed by the appearance of a new red-shifted CT band. The longer wavelength absorption band for 1, bound to TiO(2) through the proposed catecholate functionality, could also be explained based on the DFT calculations. Dynamics of the interfacial electron transfer between 1 and TiO(2) nanoparticles was investigated by studying kinetics at various wavelengths in the visible and near infrared regions. Electron injection into the conduction band of the nanoparticulate TiO(2) was confirmed by detection of the conduction band electron in TiO(2) ([e(-)](TiO(2)(CB))) and the cation radical of the adsorbed dye (1˙(+)) in real time as monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (<100 fs) electron injection was observed. Back electron transfer dynamics was determined by monitoring the decay kinetics of 1˙(+) and .     

High-Performance Dipolar Organic Dyes with an Electron-Deficient Diphenylquinoxaline Moiety in the π-Conjugation Framework for Dye-Sensitized Solar Cells

We report here the synthesis and electrochemical and photophysical properties of a series of easily prepared dipolar organic dyes and their application in dye-sensitized solar cells (DSSCs). For the six organic dyes, the molecular structures comprised a triphenylamine group as an electron donor, a cyanoacrylic acid as an electron acceptor, and an electron-deficient diphenylquinoxaline moiety integrated in the π-conjugated spacer between the electron donor and acceptor moieties. The incorporation of the electron-deficient diphenylquinoxaline moiety effectively reduces the energy gap of the dyes and broadly extends the spectral coverage. DSSCs based on dye 6 produced the best overall cell performance of 7.35?%, which translates to approximately 79?% of the intrinsic efficiency of the DSSCs based on the standard N719 dye under identical experimental conditions. The high performance of DSSCs based on dye 6 among the six dyes explored is attributed to the combined effects of high dye loading on a TiO(2) surface, rapid dye regeneration, and effective retardation of charge recombination.     

Dye-sensitized solar cells based on TiO2-B nanobelt/TiO2 nanoparticle sandwich-type photoelectrodes with controllable nanobelt length

The TiO(2)-B nanobelt (NB)/TiO(2) nanoparticle (NP) sandwich-type structure photoelectrode, with controllable nanobelt length, has been used to fabricate high-efficiency dye-sensitized solar cells (DSSCs), which combine the advantages of the rapid electron transport in TiO(2)-B NBs and the high surface area of TiO(2) NPs. The results indicate that the sandwich-type photoelectrode achieves higher photoelectrical conversion efficiency when compared with the TiO(2) nanoparticulate electrode. Increasing the length of TiO(2)-B NBs has been demonstrated to improve the photoelectric conversion efficiency (η). DSSCs with the longest (10 μm) TiO(2)-B NBs yield the highest η of 7.94%. The interfacial electron transport of DSSCs with different lengths of TiO(2)-B NBs has been quantitatively investigated using the photovoltage transient and the electrochemical impedance spectra, which demonstrates that the DSSCs with longest TiO(2)-B NBs display the highest electron collection efficiency and the fastest interfacial electron transfer.     

Effect of TiO2 colloids on the fluorescence behavior of two cyanine dyes

The photophysical properties of two typical cyanine dyes [3,3'-diethyl-9-methyl-thiacarbocyanine iodide (dye A) and anhydro-3,3'-disulfopropyl-5,5'-diphenyl-9-ethyloxacarbocyanine hydroxide (dye B)] in the absence and presence of TiO(2) colloids have been investigated by UV-visible spectroscopy, (1)H-NMR spectroscopy, fluorescence spectroscopy, fluorescence lifetime measurements, and ESR measurements. It was found from the absorption spectra and NMR results that there are two isomers in the ground state of these dyes. Steady-state fluorescence spectra show that the fluorescence intensities of dye A and dye B are enhanced and quenched by TiO(2) colloids, respectively. Time-resolved fluorescence lifetime measurements indicate that the lifetimes of dye A and dye B in the presence of TiO(2) colloids are longer and shorter than those obtained in the absence of TiO(2) colloids, respectively. ESR measurements demonstrate that the electron transfer efficiency from (1)dye B* to the conduction band of TiO(2) is much larger than that from (1)dye A* to the conduction band of TiO(2). The different fluorescence behavior of dye A and dye B can be intepreted in terms of whether phi(Tr,nr)(0)-phi(Tr,nr) (the reduction of the quantum yield for radiationless transition in the excited singlet state (1)dye* caused by the TiO(2) colloids) is larger or smaller than phi(ET) (the quantum yield of electron transfer from (1)dye* to the conduction band of TiO(2) colloids).