Electrical transport properties of [(1 - x)succinonitrile:xpoly(ethylene oxide)]-LiCF3SO3-Co[tris-(2,2'-bipyridine)]3(TFSI)2-Co[tris-(2,2'-bipyridine)]3(TFSI)3 solid redox mediators.

A solid redox mediator (solid electrolyte) with an electrical conductivity (σ25°C) greater than 10-4 S cm-1 is an essential requirement for a dye-sensitized solar cell in the harsh weather of Gulf countries. This paper reports the electrical properties of solid redox mediators prepared using highly dissociable ionic salts: Co[tris-(2,2'-bipyridine)]3(TFSI)2, Co[tris-(2,2'-bipyridine)]3(TFSI)3, and LiCF3SO3 as a source of Co2+, Co3+, and Li+ ions, respectively, in a solid matrix: [(1 - x)succinonitrile:xpoly(ethylene oxide)], where x = 0, 0.5, and 1 in weight fraction. In the presence of large size of cations (Co2+ and Co3+) and large-sized and weakly-coordinated anions (TFSI- and CF3SO3-), only the succinonitrile-poly(ethylene oxide) blend (x = 0.5) resulted in highly conductive amorphous regions with σ25°C of 4.7 × 10-4 S cm-1 for EO/Li+ = 108.4 and 3.1 × 10-4 S cm-1 for EO/Li+ = 216.8. These values are slightly lower than 1.5 × 10-3 S cm-1 for x = 0 and higher than 6.3 × 10-7 S cm-1 for x = 1. Only blend-based electrolytes exhibited a downward curve in the log σ-T-1 plot, a low value of pseudo-activation energy (0.06 eV), a high degree of transparency, and high thermal stability, making it useful for device applications.

Spectral Behavior of a Conjugated Polymer MDMO-PPV Doped with ZnO Nanoparticles: Thin Films.

The purpose of the presented study is to examine the impact of zinc oxide nanoparticles (ZnO NPs) on the spectrum features of poly [2-methoxy-5-(3',7'-dimethyloctyloxy)-1, 4-phenylenevinylene] (MDMO-PPV). The characteristics of the MDMO-PPV and doped ZnO NPS samples were assessed using several techniques. A set of solutions of MDMO-PPV in toluene that were doped with different ratio percentages of ZnO NPs was prepared to obtain thin films. Pristine and composite solutions were spin-coated on glass substrates. It was observed that MDMO-PPV had two distinct absorbance bands at 310 and 500 nm in its absorption spectrum. The UV-Vis spectrum was dramatically changed when 5% of ZnO NPs were added. The result showed a significant reduction in absorption of the band 500 nm, while 310 nm absorption increased rapidly and became more pronounced. Upon adding (10%) ZnONPs to the sample, no noticeable change was observed in the 500 nm band. However, the 310 nm band shifted towards the blue region. There is a dominant peak in the PL spectrum of MDMO-PPV in its pristine form around 575 nm and a smaller hump around 600 nm of the spectrum. The spectral profile at 600 nm and the intensity of both bands are improved by raising the ZnO NP concentration. These bands feature two vibronic transitions identified as (0-0) and (0-1). When the dopant concentration increased to the maximum dopant percentage (10%), the energy band gap values increased by 0.21 eV compared to the pristine MDMO-PPV. In addition, the refractive index (n) decreased to its lowest value of 2.30 with the presence of concentrations of ZnO NPs.

Preparation and Characterization of Poly(vinyl acetate-co-2-hydroxyethyl methacrylate) and In Vitro Application as Contact Lens for Acyclovir Delivery.

A series of poly(vinyl acetate-co-2-hydroxyethylmethacrylate)/acyclovir drug carrier systems (HEMAVAC) containing different acyclovir contents was prepared through bulk free radical polymerization of 2-hydroxyethyl methacrylate with vinyl acetate (VAc) in presence of acyclovir (ACVR) as the drug using a LED lamp in presence of camphorquinone as the photoinitiator. The structure of the drug carrier system was confirmed by FTIR and 1HNMR analysis, and the uniform dispersion of the drug particles in the carrier was proved by DSC and XRD analysis. The study of the physico-chemical properties of the prepared materials, such as the transparency, swelling capacity, wettability and optical refraction, was carried out by UV-visible analysis, a swelling test and measurement of the contact angle and the refractive index, respectively. The elastic modulus and the yield strength of the wet prepared materials were examined by dynamic mechanical analysis. The cytotoxicity of the prepared materials and cell adhesion on these systems were studied by LDH assay and the MTT test, respectively. The results obtained were comparable to those of standard lenses with a transparency of 76.90-89.51%, a swelling capacity of 42.23-81.80% by weight, a wettability of 75.95-89.04°, a refractive index of 1.4301-1.4526 and a modulus of elasticity of 0.67-1.50 MPa, depending on the ACVR content. It was also shown that these materials exhibit no significant cytotoxicity; on the other hand, they show significant cell adhesion. The in vitro dynamic release of ACVR in water revealed that the HEMAVAC drug carrier can consistently deliver uniformly adequate amounts of ACVR (5.04-36 wt%) over a long period (7 days) in two steps. It was also found that the solubility of ACVR obtained from the release process was improved by 1.4 times that obtained by direct solubility of the drug in powder form at the same temperature.

Structural, Thermal, and Electrical Properties of Poly(Ethylene Oxide)-Tetramethyl Succinonitrile Blend for Redox Mediators.

An all-solid−state dye-sensitized solar cell is one of the non-fossil fuel-based electrochemical devices for electricity generation in a high-temperature region. This device utilizes a redox mediator, which is a fast ion-conducting solid polymer electrolyte (SPE). The SPE makes the device economical, thinner, and safer in high-temperature regions. The SPE generally has a form of matrix−plasticizer−redox salts. Succinonitrile (SN) is generally employed as a plasticizer for reducing the crystallinity of poly(ethylene oxide), abbreviated as PEO, a common polymeric matrix. In the present paper, the structural and thermal properties of tetramethyl succinonitrile (TMSN) were compared with SN for its application as a solid plasticizer. TMSN and SN both are plastic crystals. TMSN has four methyl groups by replacing the hydrogen of the SN, resulting in higher molecular weight, solid−solid phase transition temperature, and melting temperature. We thoroughly studied the structural, thermal, and electrical properties of the [(1−x)PEO: xTMSN] blend for utilizing it as a matrix, where x = 0−0.25 in mole fraction. The FT-IR spectra and XRD patterns of the blends exhibited PEO-alike up to x = 0.15 mole and TMSN-alike for x > 0.15 mole. Differential scanning calorimetry revealed formation of a eutectic phase from x = 0.1 mole and phase separation from x = 0.15 mole. The blends with x = 0.1−0.15 mole had a low value of PEO crystallinity. Thermogravimetric analysis showed thermal stability of the blends up to 75 °C. The blends exhibited electrical conductivity, σ25°C more than 10−9 S cm−1, and Arrhenius behavior (activation energy, ~0.8 eV) in a temperature region, 25−50 °C.

Electrical Transport, Structural, Optical and Thermal Properties of [(1-x)Succinonitrile: xPEO]-LiTFSI-Co(bpy)3(TFSI)2-Co(bpy)3(TFSI)3 Solid Redox Mediators.

The solar cell has been considered one of the safest modes for electricity generation. In a dye-sensitized solar cell, a commonly used iodide/triiodide redox mediator inhibits back-electron transfer reactions, regenerates dyes, and reduces triiodide into iodide. The use of iodide/triiodide redox, however, imposes several problems and hence needs to be replaced by alternative redox. This paper reports the first Co2+/Co3+ solid redox mediators, prepared using [(1−x)succinonitrile: xPEO] as a matrix and LiTFSI, Co(bpy)3(TFSI)2, and Co(bpy)3(TFSI)3 as sources of ions. The electrolytes are referred to as SN_E (x = 0), Blend 1_E (x = 0.5 with the ethereal oxygen of the PEO-to-lithium ion molar ratio (EO/Li+) of 113), Blend 2_E (x = 0.5; EO/Li+ = 226), and PEO_E (x = 1; EO/Li+ = 226), which achieved electrical conductivity of 2.1 × 10−3, 4.3 × 10−4, 7.2 × 10−4, and 9.7 × 10−7 S cm−1, respectively at 25 °C. Only the blend-based polymer electrolytes exhibited the Vogel-Tamman-Fulcher-type behavior (vitreous nature) with a required low pseudo-activation energy (0.05 eV), thermal stability up to 125 °C, and transparency in UV-A, visible, and near-infrared regions. FT-IR spectroscopy demonstrated the interaction between salt and matrix in the following order: SN_E < Blend 2_E < Blend 1_E << PEO_E. The results were compared with those of acetonitrile-based liquid electrolyte, ACN_E.

Tetramethyl Succinonitrile as a Solid Plasticizer in a Poly(ethylene oxide)8 -LiI-I2 Solid Polymer Electrolyte.

Dye-sensitized solar cell (DSSC) is a promising alternative to the commercially available amorphous silicon-based solar cell because of several advantageous properties. A DSSC with a fast ion conducting solid polymer electrolyte is required for the arid atmosphere of Gulf countries. In this work, a new matrix, poly(ethylene oxide)-tetramethyl succinonitrile blend to synthesize a blend-LiI-I2 solid polymer electrolyte for the DSSC application has been proposed. The tetramethyl succinonitrile is a member of plastic crystal with a solid-solid phase transition temperature (Tpc ) of ≈71 °C and melting temperature (Tm ) of ≈170.5 °C. Its molar fraction, 0.1-0.15 is sufficient enough for synthesizing a polymer electrolyte with electrical conductivity of >10-4 S cm-1 at room temperature. This electrolyte shows Vogel-Tamman-Fulcher type behavior with a low value (≈0.083 eV) of pseudo-activation energy for easy ion transport. The results of Fourier-transform infrared spectroscopy, X-ray diffractometry, and differential scanning calorimetry studies reveal the plasticizing effect of tetramethyl succinonitrile to form an amorphous phase. This electrolyte results in a ≈661% gain in short-circuit current density and thereby a ≈552% gain in the cell efficiency (≈3.5%) with respect to the DSSC prepared with the tetramethyl succinonitrile-free electrolyte.

Reducing Amplified Spontaneous Emission Threshold in CsPbBr3 Quantum Dot Films by Controlling TiO2 Compact Layer.

Amplified spontaneous emission (ASE) threshold in CsPbBr3 quantum dot films is systematically reduced by introducing high quality TiO2 compact layer grown by atomic-layer deposition. Uniform and pinhole-free TiO2 films of thickness 10, 20 and 50 nm are used as a substrates for CsPbBr3 quantum dot films to enhance amplified spontaneous emission performance. The reduction is attributed indirectly to the improved morphology of TiO2 compact layer and subsequently CsPbBr3 active layer as grown on better quality substrates. This is quantified by the reduced roughness of the obtained films to less than 5 nm with 50 nm TiO2 substrate. Considering the used growth method for the quantum dot film, the improved substrate morphology maintains better the structure of the used quantum dots in the precursor solution. This results in better absorption and hence lower threshold of ASE. Besides that, the improved film quality results further in reducing light scattering and hence additional slight optical enhancement. The work demonstrates a potential venue to reduce the amplified spontaneous emission threshold of quantum dot films and therefore enhanced their optical performance.

Understanding the Electrical Transport-Structure Relationship and Photovoltaic Properties of a [Succinonitrile-Ionic Liquid]-LiI-I2 Redox Electrolyte.

The properties of succinonitrile-based electrolytes can be enhanced by the addition of an ionic liquid (IL). Here, we have reported the relationship between the electrical transport properties and the structure of a new [(1 - x)succinonitrile:xIL]-LiI-I2 electrolyte, where the mole fraction (x) of the IL (1-butyl-3-methyl imidazolium iodide) was varied from 0 to 40%. Compositional variation revealed the optimum conducting electrolyte (OCE) at x = 10 mol %, possessing an electrical conductivity (σ25°C) of ∼7.5 mS cm-1 with an enhancement of ∼369%. The partial replacement of succinonitrile by the IL eliminated the abrupt change in the slope of the log σ vs T -1 plot at the melting temperature of the succinonitrile-LiI-I2 system, showing the Vogel-Tamman-Fulcher-type behavior owing to molecular chain disorder. Raman spectroscopy showed the I3 - concentration nearly twice the I5 - concentration for the OCE. Vibrational spectroscopy exhibited red shifts in the νC≡N, νCH2 , νa,CC, νa,N-CH3 , and νs,N-butyl modes, indicating an interaction between succinonitrile and the IL. The area ratio A CH2 /A C≡N increased slightly for x = 10 mol % (OCE) and largely for x > 10 mol %, indicating an increase in the C-H bond length. These observations indicated that the interaction between succinonitrile and the IL was enhanced at x > 10 mol %, which decreased the electrical conductivity of these electrolytes. Owing to fast ion transport, an OCE-based dye-sensitized solar cell showed a 40-55% decrease in the charge-transfer and Warburg resistances, resulting in ∼139 and ∼122% increases in J SC and η, respectively.

Poly (2-hydroxyethylmethacrylate -co-methylmethacrylate)/Lignocaine Contact Lens Preparation, Characterization, and in vitro Release Dynamic.

2-hydroxyethyl methacrylate, methylmethacrylate, ethylene glycol dimethyl methacrylate, and lignocaine (drug) were mixed together and the monomers were copolymerized at 60 °C through a free radical polymerization in the presence of α,α'-Azoisobutyronitrile in tetrahydrofuran. A series of copolymer/drug composites with different monoacrylate monomer compositions were prepared by solvent evaporation and characterized by different methods such as nuclear magnetic resonance, differential scanning calorimetry, Fourier transform infrared, X-ray diffraction, and mechanical and optical testing. The water content in the copolymers and the cell viability test on the samples were also examined in this investigation. The results of the analyses of the properties of this drug-carrier system are promising, indicating that this material may be a potential candidate for contact lens applications. The release dynamic of this medication from the prepared drug-carrier systems was investigated in neutral pH media. The results obtained revealed that the diffusion of lignocaine through the copolymer matrix obeys the Fick model and the dynamic release can be easily controlled by the methyl methacrylate content in the copolymer.

Near-infrared squaraine co-sensitizer for high-efficiency dye-sensitized solar cells.

A combination of squaraine-based dyes (SPSQ1 and SPSQ2) and a ruthenium-based dye (N3) were chosen as co-sensitizers to construct efficient dye-sensitized solar cells. The co-sensitization of squaraine dyes with N3 enhanced their light-harvesting properties as a result of the broad spectral coverage in the region 350-800 nm. The co-sensitized solar cells based on SPSQ2 + N3 showed the highest short circuit current density of 17.10 mA cm(-2), an open circuit voltage of 0.66 V and a fill factor of 0.73, resulting in the highest power conversion efficiency of 8.2%, which is higher than that of the dye-sensitized solar cells based on the individual SPSQ1 and SPSQ2 dyes. The high power conversion efficiency of SPSQ2 + N3 was ascribed to its good light-harvesting properties, which resulted from its broader incident photon current conversion spectrum than that of the individual dyes. The high electron life time and electron recombination, which were the main causes of the higher efficiency of the device, were successfully analysed and correlated using transient absorption spectrometry and intensity-modulated photovoltage spectrometry.

Enhanced Photovoltaic Performances of Dye-Sensitized Solar Cells by Co-Sensitization of Benzothiadiazole and Squaraine-Based Dyes.

Dye-sensitized solar cells (DSSCs) based on a donor-acceptor-donor oligothienylene dye containing benzothiadiazole (T4BTD-A) were cosensitized with dyes containing cis-configured squaraine rings (HSQ3 and HSQ4). The cosensitized dyes showed incident monochromatic photon-to-current conversion efficiency (IPCE) greater than 70% in the 300-850 nm wavelength region. The individual overall conversion efficiencies of the sensitizers T4BTD-A, HSQ3, and HSQ4 were 6.4%, 4.8%, and 5.8%, respectively. Improved power conversion efficiencies of 7.0% and 7.7% were observed when T4BTD-A was cosensitized with HSQ3 and HSQ4, respectively, thanks to a significant increase in current density (JSC) for the cosensitized DSSCs. Intensity-modulated photovoltage spectroscopy results showed a longer lifetime for cosensitized T4BTD-A+HSQ3 and T4BTD-A+HSQ4 compared to that of HSQ3 and HSQ4, respectively.

Prospects of Graphene as a Potential Carrier-Transport Material in Third-Generation Solar Cells.

Third-generation solar cells are understood to be the pathway to overcoming the issues and drawbacks of the existing solar cell technologies. Since the introduction of graphene in solar cells, it has been providing attractive properties for the next generation of solar cells. Currently, there are more theoretical predictions rather than practical recognitions in third-generation solar cells. Some of the potential of graphene has been explored in organic photovoltaics (OPVs) and dye-sensitized solar cells (DSSCs), but it has yet to be fully comprehended in the recent third-generation inorganic-organic hybrid perovskite solar cells. In this review, the diverse role of graphene in third-generation OPVs and DSSCs will be deliberated to provide an insight on the prospects and challenges of graphene in inorganic-organic hybrid perovskite solar cells.

More stable and more efficient alternatives of Z-907: carbazole-based amphiphilic Ru(II) sensitizers for dye-sensitized solar cells.

Here we report two novel amphiphilic Ru(II) heteroleptic bipyridyl complexes, HD-14 and HD-15, compared to previously reported NCSU-10. We have combined the strong electron donor characteristics of carbazole and the hydrophobic nature of different long alkyl chains, C7, C18 and C2 (NCSU-10), tethered to N-carbazole to study their influence on photocurrent, photovoltage and long term stability for dye-sensitized solar cells. Photon harvesting efficiency and electron donating characteristics of carbazole-based ancillary ligands were found to be unaffected by different alkyl chain lengths. However, a slight drop in the Voc of HD-14 and HD-15 was observed compared to that of NCSU-10. It was found by nanosecond flash photolysis transient absorption (TA) measurements that the faster the dye regeneration the higher the photocurrent density response, and the dye regeneration time was found to be 2.6, 3.6, and 3.7 µs for HD-14, HD-15, and N719 dyes, respectively. The difference in the amplitude of the transient absorption (TA) signal of the oxidized dye as measured by femtosecond TA studies is in excellent agreement with the photocurrent generated, which was in the following order HD-14 > HD-15 > N719. Under 1000 h light soaking conditions, HD-15 maintained up to 98% (only 2% loss) of the initial power conversion efficiency compared to 8% loss for HD-14 and 22% loss in the power conversion efficiency for NCSU-10. HD-15 was strikingly stable to light soaking conditions when employed in the presence of an ionic liquid electrolyte, which paves the way for widespread applications of dye-sensitized solar cells with long term stability. The total power conversion efficiency (η) was 9.27% for HD-14 and 9.17% for HD-15 compared to 8.92% for N719.

A comparative study of Ru(II) cyclometallated complexes versus thiocyanated heteroleptic complexes: thermodynamic force for efficient dye regeneration in dye-sensitized solar cells and how low could it be?

Four novel Ru(II) bipyridyl complexes MH12­15 were synthesized and characterized for dye-sensitized solar cells (DSSCs). Their photovoltaic performance including incident photon-to-current conversion efficiency (IPCE), total solar-to-power conversion efficiency (η%) and ground and excited state oxidation potentials and photoelectrochemical properties were evaluated on mesoporous nanocrystalline TiO2 and compared with the benchmark N719-dye under the same experimental conditions. MH12­15 showed stronger MLCT with significantly higher molar extinction coefficient for the lower energy absorption bands at 553 nm (27,500 M(−1) cm(−1)), 554 nm (34,605 M(−1) cm(−1)), 577 nm (23,300 M(−1) cm(−1)), and 582 nm (39,000 M(−1) cm(−1)), respectively, than that of N719 (14,200 M(−1) cm(−1)). The introduction of a cyclometallated ligand in dyes MH14 and 15 improved the optical properties and red-shifts of 24 nm and 28 nm, respectively, compared to the non-cyclometallated analogs MH12 and 13. The red shift in the UV-Vis spectra of MH14 and 15 can be attributed to the destabilization of the HOMO t2g of Ru(II). However, the destabilization of the HOMO furnished an upward shift of the ground state oxidation potentials (GSOPs) of MH14 and 15 at −5.44 eV and −5.36 eV against vacuum, respectively, which resulted in a driving force of only 0.22 and 0.16 eV for regeneration of dyes MH14 and 15, respectively. In the case of NCS analogs, MH12 and 13, the GSOPs, however, were −5.56 and −5.51 eV, respectively, which produced a driving force of more than 0.25 eV for dye regeneration. The nanosecond transient absorbance measurements showed that the time needed for the oxidized forms of MH12­MH15 to regenerate the neutral dye is 6 µs, 4 µs, 13 µs and 18 µs, respectively, compared to N719 (2.3 µs). These kinetic data confirmed that the weak thermodynamic force, small negative free energy (−ΔG), for regeneration of MH14 and 15 neutral dyes makes the dye regeneration process kinetically sluggish, which contributed significantly to the loss of both photocurrent and photovoltage. This study clearly elucidated that although cyclometallation may produce significantly better light harvesting, the driving force of less than 0.25 eV is not sufficiently enough for effective dye regeneration.