Novel iminocoumarin dyes as photosensitizers for dye-sensitized solar cell

Novel iminocoumarin dyes (2a-c and 3a-c) having carboxyl and hydroxyl anchoring groups onto the dyes skeletons have been designed and synthesized for the application of dye-sensitized nanocrystalline TiO₂ solar cells (DSSCs). The photophysical and electrochemical studies showed that these iminocoumarin dyes are suitable as light harvesting sensitizers in DSSC application. The dyes having carboxyl and hydroxyl anchoring groups (2a-c) showed better efficiency when compared to the dyes having carboxyl group (3a-c) alone. The cell consisted of dye 2a generated the highest solar-to-electricity conversion efficiency (η) of 0.767% (open circuit voltage (V_oc) = 0.491 V, short circuit photocurrent density (J_sc) = 2.461 mA cm⁻², fill factor (ff) = 0.635) under simulated AM 1.5 irradiation (1000 W m⁻²) with a total semiconductor area of 0.25 cm². The corresponding incident photon-to-current conversion efficiency (IPCE) of the above cell was 21.38%. The overall low efficiency of the dyes is ascribed to the lack of light harvesting ability at longer wavelength region.     

Stable dye-sensitized solar cells based on organic chromophores and ionic liquid electrolyte

A series of polyene-diphenylaniline based organic dyes (coded as D5, D7, D9 and D11) have been reported for the application in ionic liquid electrolyte based dye-sensitized solar cells. The effects of substitution of organic dyes on the photovoltaic performance have been investigated, which show addition of methoxy groups on the triphenylamine donor group increases short-circuit current, open-circuit voltage and photovoltaic performance. A power conversion efficiency of 6.5% under AM 1.5 sunlight at 100 mW/cm² has been obtained with D11 dye in combination with a binary ionic liquid electrolyte, which when subjected to accelerated testing under one sun light soaking at 60 °C, the efficiency remained 90% of initial efficiency.     

Synthesis and characterization of trivalent metal porphyrin with NCS ligand for application in dye-sensitized solar cells

Two novel trivalent metal porphyrin dyes, P_Mn-HT-SCN and P_Ga-HT-SCN, were designed, synthesized and firstly applied in dye-sensitized solar cells (DSSCs). These two dyes possess porphyrin donor modified with manganese (III) and gallium (III) as coordination metal and NCS as the second ligand, cyanoacrylic acid as electron-accepting moiety and 4-hexylthiophene as π-spacers. Each of the porphyrin showed different adsorption behavior and saturated coverage on the TiO₂ surface. Between the two dyes, the P_Mn-HT-SCN-based DSSCs afforded the best photovoltaic performance: a short-circuit photocurrent density (J_sc) of 4.32 mA/cm², an open-circuit photovoltage (V_oc) of 0.61 V and a fill factor (FF) of 0.58, corresponding to a solar-to-electricity conversion efficiency of 1.53% under 100 mW/cm² irradiation.     

Synthesis of new low band gap dyes with BF2-azopyrrole complex and their use for dye-sensitized solar cells

The diazonium salt derived from 4-aminobenzoic acid, 4-aminophenol or 2-aminophenol reacted with half equivalent of pyrrole to afford symmetrical 2,5-bisazopyrroles. They reacted subsequently with boron trifluoride in the presence of triethylamine to afford the corresponding BF₂-azopyrrole complexes D1, D2 and D3 respectively. They were soluble and stable in nonprotic solvents such as chloroform, dichloromethane and tetrahydrofuran but unstable in protic solvents such as ethanol. Their absorption spectra were broad with optical band gap of 1.49-1.70 eV. Among these dyes D2 displayed the broader absorption spectrum with low band gap of 1.49 eV. We have utilized these complexes as photosensitizers for quasi solid state dye-sensitized solar cells (DSSCs) and achieved power conversion efficiency in the range of 4.0-6.0%. We have also found that the co-adsorption of citric acid hindered the formation of dye aggregates and might improve the electron injection efficiency leading to an enhancement in short circuit photocurrent. This work suggests that metal-free dyes based on BF₂-azopyrrole complex are promising candidates for improvement of the DSSC performance.     

Triphenylamine-substituted methanofullerene derivatives for enhanced open-circuit voltages and efficiencies in polymer solar cells

A new class of triphenylamine substituted methanofullerene derivatives, bis(4'-(diphenylamino)biphenyl-4-yl)methanofullerene (1) and the bisadduct (2), were synthesized. The incident photon to current efficiency (IPCE) studies revealed that the diphenylamino components have contribution to the photocurrent that expands the light harvesting window around 400 nm. When being blended with poly (3-hexylthiophene) (P3HT) to fabricate the solar cell, the device of P3HT:1 (1:0.7) shows high open circuit voltage (V_oc) of 0.69 V under the illumination of AM 1.5, 100 mW/cm² with high power conversion efficiency (PCE) of 3.16%, which is about 0.1 V higher than that of the corresponding [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) devices. This indicates that the arylamine substituents on 1 have played some special roles on the high V_oc performance. Similar effects are also observed for 2. The device of P3HT:2 (1:1) shows even higher V_oc of 0.87 V with the PCE of 1.83%. These results indicate that 1 and 2 are alternative high performance acceptors.     

Syntheses and photovoltaic properties of polymeric sensitizers using thiophene-based copolymer derivatives for dye-sensitized solar cells

We synthesized the thiophene-based copolymers (P(3TAF-co-3TAa)-A-n and P(3TAF-co-3TAa)-B-n) using two different kinds of thiophene monomers, (N-(3-thienylmethylene)-2-aminofluorene and 3-thiophene acetic acid), as sensitizers on the DSSCs. P(3TAF-co-3TAa)-A-n (n=1, 2, 3) was synthesized with different molar ratios (3TAF:3TAa=1:5, 1:10, 1:20) of monomers at room temperature, respectively. Also, P(3TAF-co-3TAa)-B-n (n=1, 2, 3) was synthesized with above molar ratios of monomers at 0 °C, respectively. The DSSCs devices were fabricated using the thiophene-based copolymers as sensitizers and their photovoltaic performances were measured by using a solar simulator under AM 1.5. In the DSSCs devices using polymeric sensitizers, V_oc is 0.53-0.60 V, J_sc is 1.9-4.5 mA/cm², FF is 0.51-0.63 and the power conversion efficiency is 0.63-1.53%, respectively.     

Synthesis and photovoltaic properties of an alternating phenylenevinylene copolymer with substituted-triphenylamine units along the backbone for bulk heterojunction and dye-sensitized solar cells

We have fabricated bulk heterojunction (BHJ) photovoltaic devices based on the as cast and thermally annealed P:[6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) blends and found that these devices gave power conversion efficiency (PCE) of about 1.15 and 1.60% respectively. P is a novel alternating phenylenevinylene copolymer which contains 2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid units along the backbone and was synthesized by Heck coupling. This copolymer was soluble in common organic solvents and showed long-wavelength absorption maximum at 390-420 nm with optical band gap of 1.94 eV. The improvement of PCE after thermal annealing of the device based on the P:PCBM blend was attributed to the increase in hole mobility due to the enhanced crystallinity of P induced by thermal treatment. In addition, we have fabricated BHJ photovoltaic devices based on the as cast and thermally annealed PB:P:PCBM ternary blend. PB is a low band gap alternating phenylenevinylene copolymer with BF₂-azopyrrole complex units, which has been previously synthesized in our laboratory. We found that the device based on this ternary blend exhibited higher PCE (2.56%) as compared to either P:PCBM (1.15%) or PB:PCBM (1.57%) blend. This feature was associated with the well energy level alignment of P, PB and PCBM, the higher donor-acceptor interfaces for the exciton dissociation and the improved light harvesting property of the ternary blend. The further increase in the PCE with thermally annealed ternary blend (3.48%) has been correlated with the increase in the crystallinity of both P and PB. Finally, we used copolymer P as sensitizer for quasi solid state dye-sensitized solar cell and we achieved PCE of approximately 3.78%.     

Two-dimensional regioregular polythiophenes with conjugated side chains for use in organic solar cells

We have prepared two two-dimensional polythiophenes (2D-PTs; P1 and P2) possessing alkyl-thiophene side chains by Stille coupling reactions. Optical measurements indicate that the bandgaps of P1 and P2 being 1.98 and 1.77 eV, respectively. P2 displayed a red-shift in its absorption spectrum because of the longer length of its conjugated side chains. Desirable highest occupied molecular orbital (HUMO) and lowest unoccupied molecular orbital (LUMO) energy levels were obtained from electrochemical studies, which suggested that these systems would exhibit high open-circuit voltages when blended with fullerene as electron acceptors. The hole mobility (thin film transistor (TFT) measurement) of P1 and P2 are 3.5×10⁻⁴ and 4.6×10⁻³ cm² V⁻¹ s⁻¹, respectively. A power conversion efficiency of 2.5% is obtained under simulated solar illumination (AM 1.5G, 100 mW cm⁻²) from a polymer solar cell comprising an active layer containing 25 wt% P1 and 75 wt% [6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM).     

Novel zinc porphyrin with phenylenevinylene meso-substituents: Synthesis and application in dye-sensitized solar cells

A novel zinc porphyrin, P, with phenylenevinylene segments at two opposite meso-positions and carboxyphenyl at the other two meso-positions of the porphyrin ring, was synthesized and characterized. The phenylenevinylene substituents were terminated with electron-accepting 4-nitro-α-cyanostilbene units. Elongation of the π-conjugation enhanced the solubility of P as well as broadened and strengthened the absorption spectrum. We have investigated the application of P in quasi solid state dye-sensitized solar cells (DSSCs). Under illumination intensity of 100 mW cm⁻², a power conversion efficiency of 2.90% was obtained for the DSSC based on P as sensitizer, which was significantly improved to 4.22% upon addition of deoxycholic acid (DCA) into the P solution for TiO₂ sensitization. Coadsorption of DCA decreased the dye adsorption, but significantly improved both short circuit current (J_sc) and open circuit voltage (V_oc). The breakup of π stacked aggregates might improve the electron injection yield and thus J_sc. The electrochemical impedance data indicate that the electron lifetime was improved by the coadsorption of DCA, which was attributed to the improvement in both V_oc and J_sc. The increase in J_sc has also been attributed to the reduction of the back reaction i.e., the recombination of electrons with tri-iodide ions.     

Synthesis, photophysical and photovoltaic properties of star-shaped molecules with triphenylamine as core and phenylethenylthiophene or dithienylethylene as arms

Two solution-processable star-shaped compounds, P and T ,that contain triphenylamine as core and phenylethenylthiophene or dithienylethylene, respectively, as arms were synthesized. They carry also a cyano group on the vinylene bond in the arms. These compounds showed an excellent thermal stability and relatively low (66-72 °C) glass transition temperatures. Their UV-vis spectra showed maximum at 431-459 nm with optical band gaps of 2.22-2.41 eV. They behaved as yellow-orange light emitters with photoluminescence (PL) maximum at 521-610 nm. The PL maximum of T was red shifted relative to P. Photovoltaic devices with active layers based on P (or T) and PCBM were prepared and the thin film composition and the thermal annealing treatment were screened in order to optimize the performance of the devices. The morphology of the blend films and the hole mobilities of P and T were also investigated. Photovoltaic performances of the devices with blend film containing 50 wt%/PCBM in P and T showed highest power conversion efficiencies (PCEs) 0.29% and 0.41%, respectively.     

A nickel-complex sensitiser for dye-sensitised solar cells

We report the first example of a Ni(II) complex that demonstrates sensitiser function in a Dye-Sensitised Solar Cell (DSSC). Complexes [Ni(dcbpy)(qdt)] (1), [Ni(decbpy)(qdt)] (2) and [Ni(decbpy)Cl₂] (3) (where dcbpy = 4,4′-dicarboxy-2,2′-bipyridine; decbpy = 4,4′-di(CO₂Et)-2,2′-bipyridine; and qdt = quinoxaline-2,3-dithiolate) have been prepared. Characterisation was carried out using electrochemical, spectroscopic and computational techniques. Intensive visible transitions of 1 and 2 have been assigned predominantly to Ligand-to-Ligand Charge Transfer (LLCT) from the qdt to the diimine ligand, suggesting appropriate charge separation for application in a photoelectrochemical device. TiO₂ sensitised with 2, following charge injection, processes a recombination time significantly long for photovoltaic function. In a DSSC, using redox electrolyte, photocurrents and photovoltages of 0.293 mA and 521 mV were observed, with optimum values requiring TiCl₄ post-treatment of TiO₂ and co-adsorption of Chenodeoxycholic acid (Cheno). Although photovoltaic function was observed, the low photocurrent is attributed to a short-lived excited state lifetime resulting in poor charge injection from the Ni(II) sensitiser.     

Solution processable quinacridone based materials as acceptor for organic heterojunction solar cells

Two series of novel quinacridone (QA) based materials that combined a strong absorption over a broad range in visible region with good electrical characteristics, which were used as the new electron-accepting materials for organic solar cells, are explored. Unique cyclic compounds 1-6 are synthesized by incorporating electron withdrawing groups (CN, COOH) at carbonyl position of alkyl substituted quinacridones, which lead to the compounds possessing the characteristics of solution-processed and being suitable for photovoltaic applications. Heterojunction solar cells with simple device configuration using these soluble materials as acceptor and effective donor poly (3-hexyl thiophene) (P3HT) were fabricated. The maximum power conversion efficiency (PCE) achieved in the solar cell based on compound 5 is 0.42% under simulated AM 1.5 solar irradiation with J_sc=1.80 mA cm⁻², V_oc=0.50 V and FF=47%. Although the aimed devices just exhibit moderate PCE, our results clearly suggest that the new-type electron-accepting materials different from fullerene have great potential as acceptor in heterojunction solar cell due to many advantages of the QA derivatives such as relatively inexpensive, good electrochemical stability and could be readily modified.     

Dimethyl-2H-benzimidazole based small molecules as donor materials for organic photovoltaics

Utilization of 2,2-dimethyl-2H-benzimidazole has received strong attention as the electron-deficient unit for the generation of electron donor material for organic photovoltaic cells (OPVs). This paper reports the first small organic molecules based on dimethyl-2H-benzimidazole, which can produce intramolecular charge transfer. Two soluble small organic molecules, MMM and OMO, with dimethyl-2H-benzimidazole unit were synthesized by Suzuki coupling reaction with Pd(0)-catalyst. The spectra of MMM and OMO in the solid thin films show absorption bands with maximum peaks at 374, 598 and 373, 588 nm, and the absorption onsets at 678 and 673 nm, corresponding to band gaps of 1.83 and 1.84 eV, respectively. The devices comprising MMM with PC61BM (1:3) showed a V_OC of 0.66 V, a J_SC of 2.03 mA/cm², and a fill factor (FF) of 0.27, giving a power-conversion efficiency of 0.37%.     

Novel symmetric squaraine chromophore containing triphenylamine for solution processed small molecule bulk heterojunction solar cells

New symmetrical low band-gap small molecule materials, SQ-bis[HP-HT2-TPA] and SQ-bis[HP-HT2-BT] incorporating as novel derivative of squaraine-pyrrole framework and π-extended thiophene with triphenyamine (TPA) and benzothiophene (BT) end group, have been synthesized and characterized. The effects of TPA moiety were investigated. Compared to SQ-bis[HP-HT2-BT], SQ-bis[HP-HT2-TPA] exhibited three times improved transporting property of hole carrier and four times enhanced absorptivity by more efficient intermolecular π−π interaction for high-efficiency bulk heterojunction (BHJ) device, suggesting that TPA contributes to a better hole mobility. The bulk-heterojunction photovoltaic devices fabricated with SQ-bis[HP-HT2-TPA]/C₇₁-PCBM BHJ film had an average power-conversion efficiency of 1.83%(±0.12) under 100 mW/cm², with a short-circuit current (J_sc) of 9.32 mA/cm², fill factor (FF) of 0.30, and open-circuit voltage (V_oc) of 0.65 V, which has ∼42% higher efficiency compared to SQ-bis[HP-HT2-BT]/C₇₁-PCBM BHJ films.     

Synthesis and properties of cis/trans mixtures of bis(4-hydroxyphenyl)-1,2-diphenylethylene containing sulfonated poly(ethersulfone)s proton exchange membranes

Conjugated cis/trans isomer-based polymer membranes were prepared with 15–25 mol% of bis(4-hydroxyphenyl)-1,2-diphenylethylene (BHDPE). BHDPE has a conjugated nonplanar conformation structure containing the peripheral four aromatic rings which facilitate the formation of π-π interactions. A series of sulfonated poly(ethersulfone)s (S-PBHDPE) was synthesized with concentrated sulfuric acid. The sulfonation took place selectively on the BHDPE unit, and simultaneously on the side-chain and main-chain phenyl groups. The S-PBHDPEs consisted of a 4:6 ratio of cis and trans form mixtures. The S-PBHDPE membrane structures and characteristics were evaluated by ¹H NMR spectroscopy, and their thermal stabilities evaluated. The ion exchange capacity (IEC), water uptake (WU) and proton conductivity of the membranes were evaluated as a function of the molar percentage of the sulfonic acid group. The WU of the synthesized S-PBHDPE membranes ranged from 21 to 52%, compared with 28% for Nafion 211^®. The S-PBHDPE membranes exhibited proton conductivities (80 °C, RH100) of 42.7–125.6 mS/cm, compared with 137.4 mS/cm for Nafion 211^®. The surface morphologies of S-PES 40 and S-PBHDPE 20 membranes were studied by AFM images.     

Modified synthesis of [Fe/LiF/C] nanocomposite, and its application as conversion cathode material in lithium batteries

In an attempt to enhance the energy storage capacity and discharge voltage, a new cathode material based on ferrocene and LiF for lithium-ion batteries has been explored [Fe/LiF/C] nanocomposite (1) has been synthesized by pyrolysis of a ferrocene/LiF mixture at 700 °C using a rotating quartz tube setup in a furnace. The structure and morphology of the composite were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Brunauer-Emmer-Teller (BET) analysis, Raman, and Mössbauer spectroscopy. The nanocomposite is composed of well-defined nanotubes which are interlinked by graphitic shell-type structures containing uniformly distribution of Fe, Fe-C, and LiF nanoparticles. The binder-free nanocomposite cathode showed enhanced electrochemical performance with the reversible specific capacity of 230 mAh g⁻¹ (1.3-4.3 V) at 20.8 mA g⁻¹ at room temperature. It exhibited a remarkable cyclic stability and good rate capability performances. The morphology of 1 was changed by ball milling, and the resulting nanocomposite 2 did not show any cyclic stability as a cathode. Thus, the cyclic stability and rate capability performances of 1 were attributed to its structure and morphology.     

Ni and metal aluminate mixtures for solid oxide fuel cell anode supports

Mixtures of nickel and metal aluminate (Ni–MAl₂O₄ [M = Fe, Co, Ni and Cu]) were fabricated, and their electrical conductivities, microstructures and thermal expansions were measured. During the sintering of these mixtures, MAl₂O₄ reacts with NiO to form NiAl₂O₄ and MO_x which are thought to be the reasons for the differences in the microstructures and electrical properties. Except for FeAl₂O₄, Ni–MAl₂O₄ mixtures show metallic conductivity behavior and their electrical conductivities are sufficient for cell operation. Their thermal expansion coefficients are much lower than conventional Ni-YSZ mixtures and closer to the 8YSZ electrolyte. The peak power densities of single cells supported with Ni–NiAl₂O₄ and Ni–CoAl₂O₄ are 410 and 440 mW cm⁻² at 850 °C, respectively, which are lower than 490 mW cm⁻² of Ni-YSZ. This is due to the polarization resistances of functional anode layer. The Ni–CuAl₂O₄-supported cell has no electrical performance because of Cu migration and segregation.     

Improved synthesis of a highly fluorinated boronic ester as dual functional additive for lithium-ion batteries

The electrolyte additive 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (PFPTFBB, 1) was found to have a reversible redox potential at 4.43 V vs. Li⁺/Li. This compound can function as an overcharge protection additive as well as anion receptor for lithium-ion batteries. It has drawn a great deal of interest from industry, but its use in relatively large quantities is limited by the production challenges of tetrafluorocatechol (TFC, 3), which is the key starting chemical for the synthesis of PFPTFBB. As part of a continuous effort in our research toward improving the safety of lithium-ion batteries, we have performed the synthesis of TFC and optimized its synthesis process. The X-ray single-crystal structures of TFC and the intermediate product 5,6,7,8-tetrafluoro-1,4-benzodioxane (4) during the process of PFPTFBB synthesis are reported for the first time. Also presented is the lithium ion cell performance of PFPTFBB as redox shuttle in various electrolyte systems.     

Bulk heterojunction organic photovoltaic devices based on low band gap small molecule BTD-TNP and perylene-anthracene diimide

Bulk heterojunction (BHJ) photovoltaic devices were fabricated from the blends of compounds BTD-TNP (electron donor) and P-A (electron acceptor) and characterized through current-voltage measurements under illumination. Compound BTD-TNP contains dithyenyl-benzothiadiazole central unit and cyanovinylene-p-nitrophenyl terminal moieties. Compound P-A is a symmetrical perylene-anthracene diimide with tert-butylphenoxy side groups at the 1,7-bay positions. Both the absorption spectra and the incident photon to the current conversion efficiency (IPCE) spectra of the device were extended up to 800 nm. A power conversion efficiency of 2.85% with short-circuit current density of 6.8 mA/cm², open-circuit voltage of 0.88 V and fill factor of 0.47 were obtained. It was found that the hole and electron mobility in the active layer were about 4.6×10⁻⁵ and 8.8×10⁻⁴ cm²/Vs, respectively, which indicates the fairly balanced charge transport in the device.