Optical and Electrochemical Properties of Non-Peripheral Thioaryl-Substituted Subphthalocyanine as Precursors for Dye-Sensitizer to Develop Photovoltaic Cells

Phthalocyanines-related compounds, subphthalocyanines, are the homologues consisting of three isoindole units with boron as the center. The absorption maximum of subphthalocyanines, called the Q band, appears around 560 - 630 nm, which is shifted by approximately 100 nm to shorter wavelengths compared to phthalocyanines. Subphthalocyanines are used as precursors to prepare unsymmetric phthalocyanines for ring enlargement reaction. In this decade, phthalocyanines are used for dye-sensitized solar cells (DSSCs), which require strong absorption of far-red light between 700 and 850 nm because of their highly efficiency. Non-peripheral thioaryl-substituted phthalocyanines have been synthesized. They show near-infrared absorption around 780 - 870 nm and have excellent electron transfer properties. However, their lack of affinity to basal plats inhibits their use as DSSC photosensitizer. Therefore, to synthesize unsymmetrical non-peripheral thioaryl-substituted phthalocyanines possessing good affinity to basal plates, the authors prepared subphthalocyanines having thioaryl substituents as precursors. Spectroscopic properties and electron transfer abilities to synthesize non-peripheral thioaryl-substituted subphthalocyanines were estimated using cyclic voltammetry. The Q band of non-peripheral thioaryl-substituted subphthalocyanines shows around 650 nm shifted to longer wavelength by 86 nm in comparison to subphthalocyanine. The compounds show many reduction potentials. They are acceptable electrons in the subphthalocyanine ring, meaning that the compounds have good electron transfer properties.

Efficient flexible dye-sensitized solar cells from rear illumination based on different morphologies of titanium dioxide photoanode

The TiO_(2) with nanoparticles(NPs),nanowires(NWs),nanorods(NRs)and nanotubes(NTs)structures were prepared by using a in-situ hydrothermal technique,and then proposed as a photoanode for flexible dye-sensitized solar cell(FDSSC).The influences of the morphology of TiO_(2) on the photovoltaic performances of FDSSCs were investigated.Under rear illumination of 100 mW·cm^(−2),the power conversion efficiencies of FDSSCs achieved 6.96%,7.36%,7.65%,and 7.83%with the TiO_(2) photoanodes of NPs,NWs,NRs,and NTs and PEDOT counter electrode.The FDSSCs based on TiO_(2) NRs and NTs photoanodes have higher short circuit current densities and power conversion efficiencies than that of the others.The enhanced power conversion efficiency is responsible for their nanotubes and rod-shaped ordered structures,which are more beneficial to transmission of electron and hole in semiconductor compared to the TiO_(2) nanoparticles and nanowires disordered structure.

Synthesis and Characterization of Novel Schiff Base for Enhanced Dye-Sensitized Solar Cell Photo-Response Mechanism

The efficient photo-response mechanism is one of the key factors in the commercialization of dye-sensitized solar cells in a bid to satisfy renewable energy demands. Progress in green technology has put solar energy on the front burner as a provider of clean and affordable energy for a sustainable society. We report the synthesis of a novel Schiff base with optical transparency in the visible and near IR region of the solar spectrum that can find application in the DSSCs photo-response mechanism. The synthesized crystal exhibited features that could handle some of the shortcomings of dye-sensitized solar cells which include wide band solar spectrum absorption and capability for swift charge transfer within the photoelectrodes. The synthesized Schiff base was characterized using x-ray diffractometer, UV/Visible spectrometer, Frontier transmission infrared spectrometer and conductometer. XRD data revealed the grown crystal to have an average crystallite size of 2.08 nm with average microstrain value of about 269.43. The FT-IR recorded transmission wave ѵ (CO) at 1207.7 cm−1 while dominant wave occurred at ѵ1654.9 and ѵ1592.3 cm−1 relating to ѵ (CN) stretching and ѵ (NH) bending respectively were observed. The IR spectrum revealed the bonding species and a probable molecular structure of 2,6-bis(benzyloxy)pyridine. The UV/Visible spectra convoluted to maximum peak within the near IR region suggesting that 2,6-bis(benzyloxy)pyridine can absorb both the visible and near IR region while its electrical conductivity was determined to be 4.58 µS/cm. The obtained result of the present study revealed promising characteristics of a photosensitizer that can find application in the photo-response mechanism of DSSCs.

Influence of O-O formation pathways and charge transfer mediator on lipid bilayer membrane-like photoanodes for water oxidation

Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.

Influence of TiCl_4 treatment on performance of dye-sensitized solar cell assembled with nano-TiO_2 coating deposited by vacuum cold spraying

Titanium tetrachloride (TiCl4) treatment was employed to TiO2 coating deposited on fluoride-doped tin oxide (FTO) conducting glass and indium oxide doped tin oxide (ITO) conducting glass, respectively. The nano-crystalline TiO2 coating was deposited using a composite powder composed of polyethylene glycol (PEG) and 25 nm TiO2 particles by vacuum cold spraying (VCS) process. A commercial N-719 dye was used to adsorb on the surface of TiO2 coating to prepare TiO2 electrode, which was applied to assemble dye-sensitized solar cell (DSC). The cell performance was measured under simulated solar light at an intensity of 100 mW·cm-2. Results show that with an FTO substrate the DSC composed of a VCS TiO2 electrode untreated by TiCl4 gives a short-circuit current density of 13.1 mA·cm-2 and an open circuit voltage of 0.60 V corresponding to an overall conversion efficiency of 4.4%. It is found that after TiCl4 treatment to the VCS TiO2 electrode with an FTO substrate, the short circuit current density of the cell increases by 31%, the open-circuit voltage increases by 60 mV and a higher conversion yield of 6.5% was obtained. However, when an ITO substrate is used to deposit TiO2 coating by VCS, after TiCl4 treatment, the conversion efficiency of the assembled cell reduces slightly due to corrosion of the conducting layer on the ITO glass by TiCl4.

Dye-sensitized Solar Cells with Higher J_(sc) by Using Polyvinylidene Fluoride Membrane Counter Electrodes

A flexible counter electrode(CE) for dye-sensitized solar cells(DSCs) has been fabricated using a micro-porous polyvinylidene fluoride membrane as support media and sputtered Pt as the catalytic material.Non-conventional structure DSCs have been developed by the fabricated CEs. The Pt metal was sputtered onto one surface of the membrane as the catalytic material. DSCs were assembled by attaching the Ti O2 electrode to the membrane surface without Pt coating. The membrane was with cylindrical pore geometry. It served not only as a substrate for the CE but also as a spacer for the DSC. The fabricated DSC with the flexible membrane CE showed higher photocurrent density than the conventional sandwich devices based on chemically deposited Pt/FTO glass, achieving a photovoltaic conversion efficiency of 4.43%. The results provides useful information in investigation and development of stable, low-cost, simple-design, flexible and lightweight DSCs.

Dye-sensitized TiO2@SBA-15 composites: Preparation and their application in photocatalytic desulfurization

Photocatalytic oxidation desulfurization has become a research hotspot in recent years because of mild reaction conditions, less energy consumption and high selectivity. In this paper, TiO2 was loaded onto SBA-15 molecular sieves and sensitized with organic dyes(2, 9-dichloroquinacridone, DCQ) to extend its spectral response range from ultraviolet light to visible light. The catalyst DCQ-X%TiO2@SBA-15 was characterized by BET measurements, X-ray diffraction, Fourier transform infrared spectroscopy and Ultraviolet-visible diffuse reflection spectra, and then it was applied for photocatalytic oxidation desulfurization of gasoline. The effects of different catalytic systems, TiO2 concentration, catalyst dosage, and different model sulfur compounds on catalytic desulfurization performance were investigated. Experimental results show that DCQ-TiO2@SBA-15 has a better performance than the unsensitized TiO2@SBA-15, and the desulfurization rate can reach up to 96.1% in a reaction time of 90 min.

Novel micro-ring structured ZnO photoelectrode for dye-sensitized solar cell

The micro-ring like structured zinc oxide(ZnO) film was deposited on SnO_2: F coated glass substrate by sol-gel dip-coating technique with 1.0 g polyethylene glycol(PEG) content. The surface morphology of micro-ring structured ZnO film has been confirmed by the scanning electron microscope. This ZnO film is used to fabricate the solar cell with the help of ruthenium based dye and carbon counter electrode. The photoelectric and incident photon-to-current conversion efficiency was 1.17% and 48.4%, respectively. The DSC results have been compared with ZnO films prepared without PEG contents.

Recent Progress of Counter Electrodes in Nanocrystalline Dye-sensitized Solar Cells

Dye-sensitized solar cell （DSC） consists a combination of several different materials： photoanodes with nanoparticulated semiconductors, sensitizers, electrolytes and counter electrodes （CEs）. Each materials performs specific task for the conversion of solar energy into electricity. The main function of CE is to transfer electrons to the redox electrolyte and regenerate iodide ion. The work of CE is mainly focused on the studies of the kinetic performance and stability of the traditional CEs to improve the overall efficiency of DSC, seeking novel design concepts or new materials. In this review, the development and research progress of different CE materials and their electrochemical performance, and the problems are discussed.

Preparation and performance of dye-sensitized solar cells based on ZnO-modified TiO_2 electrodes

The ZnO-modified TiO2 electrode was prepared by adding Zn（CH3COO）2·2H2O to the TiO2 colloid during the sol-gel production process, and was used in dye-sensitized solar cells （DSCs）. The open circuit voltage （Voc） and fill factor （if） of the cells were improved sig- nificantly. The performances of the ZnO-modified TiO2 electrode such as dark current, transient photocurrent, impedance, absorption spectra, and fiat band potential （Vfb） were investigated. It is found that the interface charge recombination impedance increases and Vfb shifts about 200 mV toward the cathodic potential. The effect mechanism of ZnO modification on the performance of DSCs may be that ZnO occupies the surface states of the TiO2 film.

Effect of imidazole based polymer blend electrolytes for dye-sensitized solar cells in energy harvesting window glass applications

The exploration of polymer electrolyte in the field of dye sensitized solar cell(DSSC) can contribute to increase the invention of renewable energy applications. In the present work, the influence of imidazole on the poly(vinylidene fluoride)(PVDF)–poly(methyl methacrylate)(PMMA)–Ethylene carbonate(EC)–KI–I2 polymer blend electrolytes has been evaluated. The different weight percentages of imidazole added into polymer blend electrolytes have been prepared by solution casting. The prepared films were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), thermogravimetric analysis(TGA), UV–visible spectra, photoluminescence spectra and impedance spectroscopy. The surface roughness texture of the film was analyzed by atomic force microscopy(AFM). The ionic conductivity of the optimized polymer blend electrolyte was determined by impedance measurement, which is 1.95 × 10-3 S·cm-1 at room temperature. The polymer electrolyte containing 40 wt% of imidazole content exhibits the highest photo-conversion efficiency of 3.04%under the illumination of 100 m W·cm-2. Moreover, a considerable enhancement in the stability of the DSSC device was demonstrated.

Gel electrolytes containing several kinds of particles used in quasi-solid-state dye-sensitized solar cells

Composite gel electrolytes containing several kinds of particles used as the quasi-solid-state electrolytes in dye-sensitized solar cells (DSSCs) were reported. Mesoporous particles (MCM-41) with unique structures composed of ordered nanochannels were served as a new kind of gelator for quasi-solid-state electrolytes. MCM-41, hydrophobic fumed silica Aerosil R972 and TiO2 nanopatricles P25 were dispersed into gel electrolytes respectively. The solar energy-to-electricity conversion efficiency of these cells is 4.65%, 6.85% and 5.05% respectively under 30 mW·cm-2 illumination. The preparation methods and the particles sizes exert an influence on the performance of corresponding solar cells. Owing to unique pore structures and high specific BET surface area, mesoporous silica MCM-41 was expected to have the potential to afford conducting nanochannels for redox couple diffusion.

A Bi-layer Composite Film Based on TiO_2 Hollow Spheres, P25,and Multi-walled Carbon Nanotubes for Efficient Photoanode of Dye-sensitized Solar Cell

A bi-layer photoanode for dye-sensitized solar cell(DSSC) was fabricated, in which TiO_2 hollow spheres(THSs) were designed as a scattering layer and P25/multi-walled carbon nanotubes(MWNTs) as an under-layer. The THSs were synthesized by a sacrifice template method and showed good light scattering ability as an over-layer of the photoanode. MWNTs were mixed with P25 to form an under-layer of the photoanode to improve the electron transmission ability of the photoanode. The power conversion efficiency of this kind of DSSC with bi-layer was enhanced to 5.13 %,which is 14.25 % higher than that of pure P25 DSSC.Graphical Abstract A bi-layer composite photoanode based on P25/MWNTs-THSs with improved light scattering and electron transmission, which will provide a new insight into fabrication and structure design of highly efficient dyesensitized solar cells.

Unique ZnS nanobuns decorated with reduced graphene oxide as an efficient and low-cost counter electrode for dye-sensitized solar cells

Unique ZnS nanobuns decorated with reduced graphene oxide （ROO） was synthesized and found to exhibit a synergetic effect as a highly efficient and low-cost counter electrode （CE） in dye-sensitized solar cells （DSCs）. Using this ZnS-ROO CE, a power conversion efficiency （PCE） of 7.03% was achieved. This value was 53% and 41 % higher than those of pure ZnS and ROO CEs, respectively. The ZnS-ROO nanocomposite is indeed an efficient and cost-effective Pt-like alternative for iodine reduction reaction.

Towards Improvement of Photovoltaic Performance of Aqueous Dye-sensitized Solar Cells by Tungsten-doped Mesoporous Nanobeads TiO_2 Working Electrode

Tungsten doped(W-doped) TiO_2 mesoporous nanobeads, possessing high surface area and superior scattering effect, were used for photoanode preparation. The W-doping would induce a positive shift of the TiO_2 conduction band, and enhance the driving force for electron injection and collection efficiencies. The electrochemical impedance spectra indicated a retarded charge recombination and increased electron diffusion length after W-doping. By fine-tuning the W-doping concentration to 0.25%, aqueous DSCs produced a significant improved the open circuit voltage of 712 mV and a short circuit current of 7.05 mA·cm^(-2), leading to an overall increased power conversion efficiency of 3.40% at 1 000 W·m^(-2) simulated irradiation, which is roughly 25% enhancement compared to that without W-doping photoanode.

A new D–D–π–A dye for efficient dye-sensitized solar cells

New metal-free organic dye sensitizers containing mono-triphenylamine or bis-triphenylamine as the electron donor, a thiophene as the π-conjugated system, and a cyanoacrylic acid moiety as the electron acceptor were synthesized. The optical and electrochemical properties of the dyes were investigated,and their performance as sensitizers in solar cells was evaluated. Dye-sensitized solar cells based on dye containing bis-triphenylamine as the electron donor produced a photon-to-current conversion efficiency of 6.06%（Jsc = 14.21 m A/cm;, Voc = 0.62 V, ff = 0.69） under 100 m W/cm;simulated AM 1.5 G solar irradiation（100 m W/cm;）.

DYE-SENSITIZED PHOTOPOLYMERIZATION OF METHYL METHACRYLATE INITIATED BY COUMARIN DYE/IODONIUM SALT SYSTEM

The photosensitive initiating system composed of 7-diethylamino-3-(2'-benzimidazolyl)coumarin dye (DEDC) and diphenyliodonium hexafluorophosphate (DIHP) which act as the sensitizer and the initiator respectively, can be used to initiate the polymerization of methyl methacrylate (MMA). The results showed that when exposed to visible light, coumarin dye/iodonium salt undergoes quick electron transfer from DEDC to DIHP and free radicals are produced. The visible light photoinduced reaction between DEDC and DIHP is mainly through the excited singlet state of DEDC and thus it is a little sensitive to O-2. The influence of concentration of DEDC, DIHP and MMA on the rate of photopolymerization of MMA was also investigated.

New strategy to incorporate nano-particle sized water oxidation catalyst into dye-sensitized photoelectrochemical cell for water splitting

In order to develop a new strategy to deposit nano-particle sized water oxidation catalyst based on earth abundant element to the photoanode in a photoelectrochemical cell for water splitting, Co;O;as water oxidation catalyst was prepared and subsequently modified by 3-aminopropyltriethoxysilane. The amino functionalized Co;O;catalyst was carefully characterized and then integrated to the ruthenium dye sensitized photoelectrode through fast Schiff base reaction. Cyclic voltammetry experiments in the dark confirmed that the modified Co;O;catalyst was still active toward water oxidation, which could be initiated by oxidation of the ruthenium photosensitizer. Under visible light irradiation, incorporation of the modified Co;O;catalyst resulted in dramatic enhancement of the transient photocurrent density for the photoanode, which was 8 times higher than that of without Co;O;catalyst.

Effects of structure and electronic properties of D-π-A organic dyes on photovoltaic performance of dye-sensitized solar cells

Herein,we examine the performance of dye-sensitized solar cells containing five D-π-A organic dyes designed by systematic modification of π-bridge size and geometric structure.Each dye has a simple push-pull structure with a triarylamino group as an electron donor,bithiophene-4,4-dimethyl-4 H-cyclopenta 1,2-b:5,4-b’]dithiophene(M11),4,4-dimethyl-4 H-cyclopenta[1,2-b:5,4-b’]dithiophenethiophene(M12),thiophene-4,4-dimethyl-4 H-cyclopenta[1,2-b:5,4-b’]dithiophene(M13),4,4-dimethyl-4 H-cyclopenta[1,2-b:5,4-b’]dithiophene-benzene(M14),and 4,4-dimethyl-4 H-cyclopenta[1,2-b:5,4-b’]dithiophene(M15)units asπ-bridges,and cyanoacrylic acid as an electron acceptor/anchor.The extension of theπ-bridge linkage favors wide-range absorption but,because of the concomitant molecular volume increase,hinders the efficient adsorption of dyes on the TiO_(2) film surface.Hence,higher loadings are achieved for smaller dye molecules,resulting in(i)a shift of the TiO_(2) conduction band edge to more negative values,(ii)a greater photocurrent,and(iii)suppressed charge recombination between the photoanode and the redox couple in the electrolyte.Consequently,under one-sun equivalent illumination(AM 1.5 G,100 mW/cm^(2)),the highest photovoltage,photocurrent,and conversion efficiency(η=7.19%)are observed for M15,which has the smallest molecular volume among M series dyes.

High efficiency and stable solid-state fiber dye-sensitized solar cells obtained using TiO_(2) photoanodes enhanced with metal organic frameworks

Solid-state fiber dye-sensitized solar cells(SS-FDSSCs) have been the subject of intensive attention and development in recent years. Although this field is only in its infancy, metal–organic frameworks(MOFs) are one such material that has been utilized to further improve the power conversion efficiency of solar cells. In this study, MOF-integrated DSSCs were shown to have potential in the development of solar cell devices with efficiency comparable to or better than that of conventional solar cells. The power conversion efficiency(PCE) of SS-FDSSCs was improved by embedding MOF-801 into a mesoporous-TiO_(2)(mp-TiO_(2)) layer, which was used as a photoanode in SS-FDSSCs, which are inherently flexible. The PCE of the MOF-integrated SS-FDSSCs was 6.50%, which is comparable to that of the reference devices(4.19%).The MOF-801 enhanced SS-FDSSCs decreased the series resistance(R_(s)) value, resulting in effective electron extraction with improved short-circuit current density(J_(SC)), while also increasing the shunt resistance(R_(sh)) value to prevent the recombination of photo-induced electrons. The result is an improved fill factor and, consequently, a higher value for the PCE.