Effect of regio-specific arylamine substitution on novel π-extended zinc salophen complexes: density functional and time-dependent density functional study on DSSC applications.

A series of π-extended salophen-type Schiff-base zinc(ii) complexes, e.g., zinc-salophen complexes (ZSC), were investigated toward potential applications for dye-sensitized solar cells. The ZSC dyes adopt linear-, X-, or π-shaped geometries either with the functionalization of 1 donor/1 acceptor or 2 donors/2 acceptors to achieve a push-pull type molecular structure. The frontier molecular orbitals, light-harvesting properties as well as charge transfer characters against regio-specific substitution of donor/acceptor groups were studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results reveal that all ZSC dyes of D-ZnS-π-A geometry (where D, S, and A denote to donor, salophen ligand, and acceptor, respectively) exhibit relatively lower HOMO energy compared to the structurally resembled porphyrin dye YD2-o-C8. Natural transition orbital (NTO) and electron-hole separation (EHS) approaches clearly differentiate the linear type YD-series dyes from CL-, AJ1-, and AJ2-series dyes because of poor charge transfer (CT) properties. In contrast, the π-shaped AJ2-series and X-shaped AJ1-series dyes outperform the others in a manner of stronger CT characteristics, broadened UV-vis absorption as well as tunable bandgap simply via substitution of p-ethynylbenzoic acids (EBAs) and arylamine donors at salophen 7,8- and 2,3,12,13-positions, respectively. Both EHS and calculated exciton binding energies suggest the strength of CT character for ZSC dyes with an amino donor in the trend TPA > AN > DPA. This work has provided clear illustration toward molecular design of efficient dyes featuring a zinc-salophen backbone.

Thieno[3,4-b]thiophene-based organic dyes for dye-sensitized solar cells.

New dipolar sensitizers containing an ethyl thieno[3,4-b]thiophene-2-carboxylate (ETTC) entity in the conjugated spacer have been synthesized in two isomeric forms. These compounds were used as the sensitizers of n-type dye-sensitized solar cells (DSSCs). The best conversion efficiency (5.31%) reaches approximately 70% of the N719-based (7.41%) DSSC fabricated and measured under similar conditions. The ETTC-containing compounds exhibit a bathochromic shift of the absorption compared to their thiophene congeners due to the quinoid effect, however, charge-trapping at the ester group of ETTC was found to jeopardize the electron injection and lower the cell efficiency. Charge trapping is alleviated as the ester group of ETTC is replaced with a hydrogen atom, as evidenced from the theoretical computation.

Effect of Thiophene Insertion on X-Shaped Anthracene-Based Hole-Transporting Materials in Perovskite Solar Cells.

In this work, two novel tetra-substituted X-shaped molecules X1 and X2 that were constructed with anthracene as the central core and arylamine as the donor groups have been synthesized. The HTMs X1 and X2 were synthesized in two steps from industrially accessible and moderately reasonable beginning reagents. These new HTMs are described in terms of utilization of light absorption, energy level, thermal properties, hole mobility (µh), and film-forming property. The photovoltaic performances of these HTMs were effectively assessed in perovskite solar cells (PSCs). The devices based on these HTMs accomplished an overall efficiency of 16.10% for X1 and 10.25% for X2 under standard conditions (AM 1.5 G and 100 mW cm-2). This precise investigation provides another perspective on the use of HTMs in PSCs with various device configurations.

Heteroleptic ruthenium sensitizers that contain an ancillary bipyridine ligand tethered with hydrocarbon chains for efficient dye-sensitized solar cells.

New heteroleptic ruthenium complexes have been synthesized and used as the sensitizers for dye-sensitized solar cells (DSSCs). The ancillary bipyridine ligand contains rigid aromatic segments (fluorene-, carbazole-, or dithieno[3,2-b:2',3'-d]pyrrole-substituted bipyridine) tethered with a hydrophobic hexyl substituent. The conjugated aromatic segment results in significant bathochromic shift and hyperchromic effects in these complexes compared with Z907 (cis-[RuLL'(NCS)(2)]; L=4,4'-dicarboxylic acid-2,2'-bipyridine, L'=4,4'-dinonyl-2,2'- bipyridine). The long hydrocarbon chains help to suppress the dark current if appropriately disposed. DSSCs that use these complexes exhibit very impressive conversion efficiencies (5.94 to 6.91 %) that surpass that of Z907-based (6.36 %) DSSCs and are comparable with that of N719-based standard cells (7.13 %; N719=cis-di(thiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium)) fabricated and measured under similar conditions (active area: 0.5×0.5 cm(2); AM 1.5 sunlight).

Dipolar compounds containing fluorene and a heteroaromatic ring as the conjugating bridge for high-performance dye-sensitized solar cells.

A novel series of dipolar organic dyes containing diarylamine as the electron donor, 2-cyanoacrylic acid as the electron acceptor, and fluorene and a heteroaromatic ring as the conjugating bridge have been developed and characterized. These metal-free dyes exhibited very high molar extinction coefficients in the electronic absorption spectra and have been successfully fabricated as efficient nanocrystalline TiO(2) dye-sensitized solar cells (DSSCs). The solar-energy-to-electricity conversion efficiencies of DSSCs ranged from 4.92 to 6.88%, which reached 68-96% of a standard device of N719 fabricated and measured under the same conditions. With a TiO(2) film thickness of 6 microm, DSSCs based on these dyes had photocurrents surpassing that of the N719-based device. DFT computation results on these dyes also provide detailed structural information in connection with their high cell performance.

tert-Butylpyridine Coordination with [Cu(dmp)2]2+/+ Redox Couple and Its Connection to the Stability of the Dye-Sensitized Solar Cell.

Cu(I)/(II) complex redox couples in dye-sensitized solar cell (DSSC) are of particular interest because of their low reorganization energy between Cu(I) and Cu(II), which minimizes the potential loss during sensitizer regeneration, thus allowing the open-circuit voltage of the device to go over 1.0 V. However, Cu(I)/(II)-based redox couples are reported to coordinate with 4-tert-butylpyridine (TBP), which is a standard additive in the electrolyte, and this is believed to account for the poor durability of a Cu(I)/(II)-based DSSCs. Despite TBP coordination on Cu(I)/(II) complexes are confirmed in the literature, its detailed mechanism is yet to be directly proven. In addition, how TBP coordination with Cu(I)/(II) complexes affects the stability of the device is never reported. Here, we choose bis(2,9-dimethyl-1,10-phenanthroline) copper(I)/(II) ([Cu(dmp)22+/+]) as the modeling redox couple to investigate its interaction with TBP. It is found that [Cu(dmp)2+] is resistive to TBP coordination but could form three new TBP-coordinated compounds. Moreover, it is also confirmed their electrochemical activity on Pt catalyst and mass transfer capability are both demoted significantly. As a result, serious fill factor loss is observed on the stability trail while short-circuit current density and open-circuit voltage are relatively unaffected. This unique degradation pattern may resemble a feature of Cu(I)/(II)-based redox couple after TBP poisoning.

Reactions of ruthenium vinylidene and acetylide complexes containing trichloromethyl groups: preparation of a cyclobutenonyl complex by solid-state photolysis.

Solid-state route to a cyclobutenone: Ruthenium perchlorocyclobutenonyl complex 2 is obtained by solid-state photoisomerization of ruthenium trichloroacetyl acetylide complex 1. The four-membered ring is sufficiently robust that transfer of the intact ligand could be readily achieved in a reaction of 2 with an enyne. Cyclobutenedionyl complex 3 was obtained by hydrolysis of 2 in H(2)O/THF.New reactions were observed for the cationic gamma-hydroxyvinylidene complex [Ru(2)]==C==CHC(OH)(CCl(3))(2) (+) (2, [Ru(2)]=CpRu(PPh(3))(2)). A rare chloroform elimination was observed when 2 was treated with nBu(4)NOH to give neutral acetylide complex [Ru(2)]--C[triple chemical bond]CC(==O)CCl(3) (3). Solid-state photoinduced isomerization of 3 generated ruthenium perchlorocyclobutenonyl complex [Ru(2)]--C(4)Cl(3)O (4) in high yield. This transformation was analyzed by DFT calculations, and 4 was found to be 4.22 kcal mol(-1) more stable in terms of Gibbs free energy than 3. In the coupling reaction of 4 with 2-methyl-1-buten-3-yne the four-membered cyclic ligand is transferred to the enyne to give substituted eta(3)-butadienyl complex 5 containing a cyclobutenonyl group. This coupling product could be removed from the metal by HCl. Deprotonation of 2 gave gamma-hydroxyacetylide complex [Ru(2)]--C[triple chemical bond]CC(OH)(CCl(3))(2) (9). In the photolysis of 9 phosphine dissociation is followed by addition of HCl to give neutral vinylidene complex Cl[Ru(1)]==C==CHC(OH)(CCl(3))(2) (10, [Ru(1)]=Cp(PPh(3))Ru). Complex 4 catalyzed the coupling reaction of dimethyl acetylenedicarboxylate with styrene yielding the diene PhCH==CHC(CO(2)Me)==CHCO(2)Me. Solid-state structures of 3-6 and 10 were determined by single-crystal X-ray diffraction analysis.

Synthesis and Characterization of Novel ß-Bis( N, N-diarylamino)-Substituted Porphyrin for Dye-Sensitized Solar Cells under 1 sun and Dim Light Conditions.

In this work, we have synthesized a novel porphyrin dye named SK7, which contains two N, N-diarylamino moieties at two ß-positions as electron-donating units and one carboxy phenylethynyl moiety at the meso-position as an electron-withdrawing, anchoring group. This novel dye was tested for the application in dye-sensitized solar cells. The light-harvesting behavior of SK7 and YD2 was investigated using UV-vis absorption and density functional calculation. The electron transport properties at the TiO2/dye/electrolyte interface for SK7- and YD2-based devices were evaluated by electrochemical impedance spectroscopy. X-ray crystallographic characterization was conducted to understand the influence of two N, N-diarylamino units at two ß-positions. The power conversion efficiencies of ca. 6.54% under 1 sun illumination (AM 1.5G) and ca. 19.72% under a T5 light source were noted for the SK7 dye. The performance of SK7 is comparable to that of dye YD2, which contains only one N, N-diarylamino moiety at the meso-position (ca. 7.78 and 20.00% under 1 sun and T5 light, respectively).

Structurally Simple and Easily Accessible Perylenes for Dye-Sensitized Solar Cells Applicable to Both 1 Sun and Dim-Light Environments.

The need for low-cost and highly efficient dyes for dye-sensitized solar cells under both the sunlight and dim light environments is growing. We have devised GJ-series push-pull organic dyes which require only four synthesis steps. These dyes feature a linear molecular structure of donor-perylene-ethynylene-arylcarboxylic acid, where donor represents N,N-diarylamino group and arylcarboxylic groups represent benzoic, thienocarboxylic, 2-cyano-3-phenylacrylic, 2-cyano-3-thienoacrylic, and 4-benzo[c][1,2,5]thiadiazol-4-yl-benzoic groups. In this study, we demonstrated that a dye without tedious and time-consuming synthesis efforts can perform efficiently. Under the illumination of AM1.5G simulated sunlight, the benzothiadiazole-benzoic-containing GJ-BP dye shows the best power conversion efficiency (PCE) of 6.16% with VOC of 0.70 V and JSC of 11.88 mA cm-2 using liquid iodide-based electrolyte. It also shows high performance in converting light of 6000 lx light intensity, that is, incident power of ca. 1.75 mW cm-2, to power output of 0.28 mW cm-2 which equals a PCE of 15.79%. Interestingly, the benzoic-containing dye GJ-P with a simple molecular structure has comparable performance in generating power output of 0.26 mW cm-2 (PCE of 15.01%) under the same condition and is potentially viable toward future application.

Influence of Phenylethynylene of Push-Pull Zinc Porphyrins on the Photovoltaic Performance.

A series of zinc porphyrin dyes YD22-YD28 were synthesized and used for dye-sensitized solar cells. Dyes YD26-YD28 consist of zinc porphyrin (ZnP) as core unit, arylamine (Am) as electron-donating group, and p-ethynylbenzoic acid (EBA) as an electron-withdrawing/-anchoring group. The dyes YD22-YD25 contain additional phenylethynylene group (PE) bridged between Am and ZnP units. The influence of the PE unit on molecular properties as well as photovoltaic performances were investigated via photophysical and electrochemical studies and density functional calculations. With the insertion of PE unit, the dyes YD22-YD25 possess better light-harvesting properties in terms of significantly red-shifted Q-band absorption. The conversion efficiencies for dyes YD22-YD25 are better than those of dyes YD26-YD28 owing to larger J(SC) output. Natural transition orbitals and Mulliken charge analysis were used to analyze the electron injection efficiency for porphyrin dyes upon time-dependent DFT calculations. The results indicated that insertion of additional PE unit is beneficial to higher J(SC) by means of improved light-harvesting property due to broadened and red-shifted absorption.

Naphtho[2,3-c][1,2,5]thiadiazole and 2H-Naphtho[2,3-d][1,2,3]triazole-Containing D-A-π-A Conjugated Organic Dyes for Dye-Sensitized Solar Cells.

Dipolar dyes comprising an arylamine as the electron donor, a cyanoacrylic acid as electron acceptor, and an electron deficient naphtho[2,3-c][1,2,5]thiadiazole (NTD) or naphtho[2,3-d][1,2,3]triazole (NTz) entity in the conjugated spacer, were developed and used as the sensitizers in dye-sensitized solar cells (DSSCs). The introduction of the NTD unit into the molecular frame distinctly narrows the HOMO/LUMO gap with electronic absorption extending to >650 nm. However, significant charge trapping and dye aggregation were found in these dyes. Under standard global AM 1.5 G illumination, the best cell photovoltaic performance achieved 6.37 and 7.53% (∼94% relative to N719-based standard cell) without and with chenodeoxycholic acid (CDCA) coadsorbent, respectively. Without CDCA, the NTz dyes have higher power conversion efficiency (7.23%) than NTD dyes due to less charge trapping, dye aggregation, and better dark current suppression.

Incorporating a new 2H-[1,2,3]triazolo[4,5-c]pyridine moiety to construct D-A-π-A organic sensitizers for high performance solar cells.

Two new organic dyes (PTN1 and NPT1) of the configuration D-A-π-A, based on 2H-[1,2,3]triazolo[4,5-c]pyridine (PT) as a central linker, have been synthesized and used as the sensitizers for dye-sensitized solar cells. Compared with pyridal[2,1,3]thiadiazole-containing congeners, the new dyes have conversion efficiencies nearly 1 order higher due to alleviation of charge trapping. The best conversion efficiency of the cell reaches 6.05% (under AM 1.5G irradiation). Upon addition of the coadsorbent CDCA, the efficiency is boosted to 6.76%, which reaches ∼90% of the standard based on N719.

Dye-sensitized solar cells based on (donor-π-acceptor)2 dyes with dithiafulvalene as the donor.

Dipolar metal-free sensitizers (D-π-A; D=donor, π=conjugated bridge, A=acceptor) consisting of a dithiafulvalene (DTF) unit as the electron donor, a benzene, thiophene, or fluorene moiety as the conjugated spacer, and 2-cyanoacrylic acid as the electron acceptor have been synthesized. Dimeric congeners of these dyes, (D-π-A)(2), were also synthesized through iodine-induced dimerization of an appropriate DTF-containing segment. Dye-sensitized solar cells (DSSCs) with the new dyes as the sensitizers have cell efficiencies that range from 2.11 to 5.24 %. In addition to better light harvesting, more effective suppression of the dark current than the D-π-A dyes is possible with the (D-π-A)(2) dyes.

High-performance dye-sensitized solar cells based on phenothiazine dyes containing double anchors and thiophene spacers.

A series of new push-pull phenothiazine-based dyes (HL1-HL4) featuring various π spacers (thiophene, 3-hexylthiophene, 4-hexyl-2,2'-bithiophene) and double acceptors/anchors have been synthesized, characterized, and used as sensitizers for dye-sensitized solar cells (DSSCs). Among them, the best conversion efficiency (7.31%) reaches approximately 99% of the N719-based (7.38%) DSSCs fabricated and measured under similar conditions. The dyes with two anchors have more efficient interfacial charge generation and transport compared with their congeners with only single anchor. Incorporation of hexyl chains into the π-conjugated spacer of these double-anchoring dyes can efficiently suppress dye aggregation and reduce charge recombination.

Organic dyes incorporating the dithieno[3',2':3,4;2″,3″:5,6]benzo[1,2-c]furazan moiety for dye-sensitized solar cells.

New D-π-A'-π-A type sensitizers (JH dyes), comprised arylamine as the electron donor, dithieno[3',2':3,4;2″,3″:5,6]benzo[1,2-c]furazan (DTBF) in the conjugated spacer, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized. The JH dyes have broad absorption spectra covering the range of 350 to 600 nm with the highest molar extinction coefficient up to >40 000 M(-1) cm(-1). The dye-sensitized solar cells (DSSCs) fabricated from the dyes exhibited light-to-electricity conversions ranging from 1.42 to 6.18% under simulated AM 1.5 G illumination. Upon adding 10 mM CDCA as the coadsorbent, the best performance cell has the power conversion efficiency of 7.33%, which is close to that of N719-based standard DSSC (7.56%).

Turbulent-PSO-Based Fuzzy Image Filter With No-Reference Measures for High-Density Impulse Noise.

Digital images are often corrupted by impulsive noise during data acquisition, transmission, and processing. This paper presents a turbulent particle swarm optimization (PSO) (TPSO)-based fuzzy filtering (or TPFF for short) approach to remove impulse noise from highly corrupted images. The proposed fuzzy filter contains a parallel fuzzy inference mechanism, a fuzzy mean process, and a fuzzy composition process. To a certain extent, the TPFF is an improved and online version of those genetic-based algorithms which had attracted a number of works during the past years. As the PSO is renowned for its ability of achieving success rate and solution quality, the superiority of the TPFF is almost for sure. In particular, by using a no-reference Q metric, the TPSO learning is sufficient to optimize the parameters necessitated by the TPFF. Therefore, the proposed fuzzy filter can cope with practical situations where the assumption of the existence of the "ground-truth" reference does not hold. The experimental results confirm that the TPFF attains an excellent quality of restored images in terms of peak signal-to-noise ratio, mean square error, and mean absolute error even when the noise rate is above 0.5 and without the aid of noise-free images.

Benzotriazole-containing D-π-A conjugated organic dyes for dye-sensitized solar cells.

A series of metal-free benzotriazole-based dipolar dyes have been developed as sensitizers for dye-sensitized solar cells (DSSCs). Different heteroaromatic rings such as furan, thiophene, and selenophene, were used in combination with benzotriazole as the conjugated spacer group. Light harvesting, charge recombination, and electron injection of the cells fabricated are affected by the heteroaromatic ring used in the spacer. The DSSC with the thiophene-containing dye has the highest conversion efficiency of 6.20%, which reaches 85% of the standard cell based on N719.

Naphthyl and thienyl units as bridges for metal-free dye-sensitized solar cells.

A series of new organic dyes, comprising a naphthyl moiety as a π-conjugated bridge, different amines as donors, and a cyanoacrylic acid group as an electron acceptor and anchoring group, have been designed and synthesized for applications in dye-sensitized solar cells (DSSCs). One of the compounds was also characterized by single-crystal X-ray structural analysis. All of the dyes exhibited maximum absorptions in the range of 371-441 nm. The short-circuit photocurrent density, open-circuit voltage, and fill factor (FF) values of the devices are in the range of 6.13-10.90 mA cm(-2), 0.62-0.69 V, and 0.62-0.67, respectively, corresponding to an overall conversion efficiency of 2.76-4.55%. The conversion efficiency reached 38-62% of that of a N719-based device (7.31%) fabricated and measured under similar conditions. Steric congestion between the naphthyl and aromatic moieties jeopardizes charge transfer from the donor to the acceptor. Insertion of an alkenyl entity between the naphthyl entity and the aromatic ring alleviates steric congestion and leads to longer wavelength electronic absorption spectra.

BODIPY dyes with ß-conjugation and their applications for high-efficiency inverted small molecule solar cells.

Small molecule BODIPY dyes incorporating conjugated substituents at the ß sites have been synthesized. Solution processed inverted bulk heterojunction cells were fabricated from the blends of the dyes and PC(71)BM. The cells exhibited very high open-circuit voltages (>0.9 V) and a high conversion efficiency of 3.22% has been achieved.

Squaraine-arylamine sensitizers for highly efficient p-type dye-sensitized solar cells.

New near-IR (NIR) squaraine dyes (p-SQ1 and p-SQ2) containing one and two anchoring groups were synthesized and used as the sensitizers of p-type DSSCs. The dye (0.113%) with two anchoring groups (p-SQ2) shows better performance than the dye (0.053%) with only one anchoring group (p-SQ1). Cosensitized p-type DSSCs using two dyes with complementary absorption were tested. They have broadened IPCE spectra and good cell performance.