Effects of different acceptors in phenothiazine-triphenylamine dyes on the optical, electrochemical, and photovoltaic properties

In dye-sensitized solar cells (DSSCs), as the excited electrons from dye molecules are injected to the conduction band of semiconductor film through the acceptor moieties, the acceptor groups have significant influences on the photovoltaic properties of the dyes. In this paper, the effects of different acceptor groups (cyanoacetic acid and rhodanine-3-acetic acid) in two phenothiazine-triphenylamine dyes (PTZ-1 and PTZ-2) on the optical, electrochemical properties and photovoltaic performances were studied. In comparison with PTZ-2, the photovoltaic performance of PTZ-1 is significantly improved by replacing rhodanine-3-acetic acid to cyanoacetic acid. The conversion efficiency of solar cell based on the PTZ-1 is increased about 110%. The lower efficiency of solar cell based on PTZ-2 is mainly because the delocalization of the excited state is broken between the 4-oxo-2-thioxothiazolidine ring and the acetic acid, which affects the electron injection from PTZ-2 to the conduction band of TiO₂.     

Organic dyes with oligo-n-hexylthiophene for dye-sensitized solar cells: Relation between chemical structure of donor and photovoltaic performance

Organic dyes with the oligohexylthiophene linkage having several donor parts, carbazole, indole, and indoline, were newly synthesized as sensitizers for dye-sensitized solar cells. The carbazole was most efficient donor moiety for DSSCs among these dyes with the oligothiophene linkage. Carbazole dyes were adsorbed with larger amount of molecules on the TiO₂ film than both indole dyes and indoline dyes. Therefore, both the V_OC and the electron lifetime of DSSCs with the carbazole dyes were highly observed. The decreasing of J_SC of DSSCs with indole and indoline dyes also caused by the reducing the adsorption amount of dyes.     

Effect of side chain substituents on the electron injection abilities of unsymmetrical perylene diimide dyes

Three near-infrared (NIR) absorbing unsymmetrical perylene diimide D-A-D type dyes containing 6-undecanoxy as donor group were utilized in dye-sensitized nanocrystalline TiO₂ solar cells. Structure of the acceptor side of the molecules were improved by adding 4-[2-methyl-5-(cyanoacrylic acid)-3-thienyl]-phenyl (V), 3-carboxy-2-pyridil (VI) and 3-carboxy-2-pyrazyl (VII) moieties attached to one of the N-side of the dye. The relationship between the molecular structure of the acceptor sites of the dyes and the photovoltaic performances were discussed. Electrochemical measurements indicated that band gaps of the dyes were energetically favorable for electron injection from the excited state of the dyes to the conduction band of TiO₂ nanoparticles. However, three dyes gave lower conversion efficiency on DSSC applications. Strong electron-withdrawing nature of perylene core might not permit to transfer the photo-generated electrons to the carboxyl groups anchoring to TiO₂ surface, and then solar-to-electricity conversion efficiencies of the dyes were reduced.     

Enhancement of the photoelectric performance of dye-sensitized solar cells using Ag-doped TiO<Subscript>2</Subscript> nanofibers in a TiO<Subscript>2</Subscript> film as electrode

For high solar conversion efficiency of dye-sensitized solar cells [DSSCs], TiO₂ nanofiber [TN] and Ag-doped TiO₂ nanofiber [ATN] have been extended to be included in TiO₂ films to increase the amount of dye loading for a higher short-circuit current. The ATN was used on affected DSSCs to increase the open circuit voltage. This process had enhanced the exit in dye molecules which were rapidly split into electrons, and the DSSCs with ATN stop the recombination of the electronic process. The conversion efficiency of TiO₂ photoelectrode-based DSSCs was 4.74%; it was increased to 6.13% after adding 5 wt.% ATN into TiO₂ films. The electron lifetime of DSSCs with ATN increased from 0.29 to 0.34 s and that electron recombination was reduced.     

Triphenylamine-based organic dyes containing benzimidazole derivatives for dye-sensitized solar cells

The synthesis and application to dye-sensitized solar cells of two new triphenylamine-based organic dyes containing benzimidazole derivatives as secondary donors together with a simple triphenylamine derived dye for the purpose of comparison is reported. The photophysical and electrochemical properties of the dyes were investigated by UV–vis spectroscopy and cyclic voltammetry. The introduction of benzimidazole derivatives in the phenyl ring of the triphenylamine core increases the molar extinction coefficients and λ_max because of the extension of the π-conjugation structures of the dyes. Overall conversion efficiencies of ∼2.5% under full sunlight (AM 1.5G, 100 mW cm⁻²) irradiation were obtained for DSSCs based on these new dyes, under the same conditions, the reference dye and di-tetrabutylammonium cis-bis(isothiocyanato) bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium(II) (N719) gave overall conversion efficiencies of 1.23% and 5.61%, respectively. Our findings demonstrate that the introduction of benzimidazole derivatives as secondary donors in triphenylamine-based dye can improve their photovoltaic performance compared to the unsubstituted reference dye in DSSCs.     

Variation of carboxylate-functionalized cyanine dyes to produce efficient spectral sensitization of nanocrystalline solar cells

The sensitizing properties of cyanine dyes in dye-sensitized nanocrystalline TiO₂ solar cells are shown to be controlled by the character of the carboxyl functions used to attach the molecules to the surface. These tether functions affect the degree of aggregation of the subject cyanine dyes attached to TiO₂ as well as the short circuit photocurrents they produce in these solar cells. Use of two carbons, acetic acid linkages, on the dye results in performance in a sensitized solar cell comparable with a control ruthenium complex, in contrast to the greatly diminished performance of dyes with longer, methylbenzoic acid linkages.     

Dye-sensitized solar cells based on double-layered TiO2 composite films and enhanced photovoltaic performance

Dye-sensitized solar cells (DSSCs) are fabricated based on double-layered composite films of TiO₂ nanoparticles and hollow spheres. The photoelectric conversion performances of DSSCs based on nanoparticles/nanoparticles (PP), hollow spheres/hollow spheres (HH), hollow spheres/nanoparticles (HP), and nanoparticles/hollow spheres (PH) double-layered films are investigated, and their photo-electric conversion efficiencies are 4.33, 4.72, 4.93 and 5.28%, respectively. The enhanced performance of TiO₂ nanoparticles/hollow spheres double-layered composite film solar cells can be attributed to the combined effect of following factors. The light scattering of overlayer hollow spheres enhances harvesting light of the DSSCs and the underlayer TiO₂ nanoparticle layer ensures good electronic contact between film electrode and the F-doped tin oxide (FTO) glass substrate. Furthermore, the high surface areas and pore volume of TiO₂ hollow spheres are respectively beneficial to adsorption of dye molecules and transfer of electrolyte solution.     

Organic dyes incorporating low-band-gap chromophores based on π-extended benzothiadiazole for dye-sensitized solar cells

A series of new π-conjugated organic dyes (HKK-BTZ1, HKK-BTZ2, HKK-BTZ3 and HKK-BTZ4), comprising triphenylamine (TPA) moieties as the electron donor and benzothiadiazole moieties as the electron acceptor/anchoring groups, was synthesized for the use in dye-sensitized solar cells (DSSCs). TPA units are bridged to benzothiadiazole with single(S), double(D) and triple bonds(T) in different derivatives. And HKK-BTZ1 was modified by introducing alkoxy group of TPA unit, because the bulky alkoxy group is a strong donating group for the more red shift and for reducing aggregation of dyes in TiO₂ film. The structure-property relationship was investigated. Under standard global AM 1.5 G illumination, a maximum photo-to-electron conversion efficiency of 7.30% was achieved with the DSSC based on dye HKK-BTZ4 (J_SC = 17.9 mA/cm⁻², V_OC = 0.62 V, FF = 0.66), while the Ru dye N719-sensitized DSSC showed an efficiency of 7.82% with a J_SC of 17.5 mA/cm⁻², a V_OC of 0.62 V, and a FF of 0.72.     

Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells

Four porphyrin dyes, incorporating multi-alkylthienyl appended porphyrins as the electron donor, the 2-cyanoacrylic acid as the electron acceptor, and different π-conjugated spacer, have been synthesized for dye-sensitized solar cells (DSSCs). All the porphyrin dyes studied in this work exhibit red-shifted and broadened electronic spectra respect to the reference P_Zn as expected. By the introduction of thienyl groups at the meso-positions, the energy level of E_ox (excited-state oxidation potentials) is significantly shifted to the positive compared with the reference P_Zn, indicating a decreased HOMO–LUMO gap. The highest power conversion efficiency of the four dyes based on DSSCs reached 5.71% under AM 1.5 G irradiation.     

Preparation of TiO<Subscript>2</Subscript> nanotube/nanoparticle composite particles and their applications in dye-sensitized solar cells

Efficiency of dye-sensitized solar cells [DSSCs] was enhanced by combining the use of TiO₂ nanotubes [TNTs] and nanoparticles. TNTs were fabricated by a sol-gel method, and TiO₂ powders were produced through an alkali hydrothermal transformation. DSSCs were constructed using TNTs and TiO₂ nanoparticles at various weight percentages. TNTs and TiO₂ nanoparticles were coated onto FTO glass by the screen printing method. The DSSCs were fabricated using ruthenium(II) (N-719) and electrolyte (I₃/I₃ ^-) dyes. The crystalline structure and morphology were characterized by X-ray diffraction and using a scanning electron microscope. The absorption spectra were measured using an UV-Vis spectrometer. The incident photocurrent conversion efficiency was measured using a solar simulator (100 mW/cm²). The DSSCs based on TNT/TiO₂ nanoparticle hybrids showed better photovoltaic performance than cells made purely of TiO₂ nanoparticles.     

Performance improvement of dye-sensitizing solar cell by semi-rigid triarylamine-based donors

Novel organic dyes (IDB and ISB dyes), which contain 5-phenyl-iminodibenzyl (IDB) and 5-phenyl-iminostilbene (ISB) as electron donors and a cyanoacrylic acid moiety as an electron acceptor and an anchoring group, connected with a thiophene as a π-conjugated system, have been synthesized and used as the sensitizers for dye-sensitized solar cells (DSSCs). The photophysical and electrochemical properties of the dyes were investigated by absorption spectrometry, cyclic voltammetry and density functional theory calculations. As demonstrated, the IDB and ISB unit exhibited stronger electron-donating ability and broader absorption spectra when coated onto TiO₂. The DSSC based on ISB-2 consisting of ISB unit produced 5.83% of η (J_sc = 13.14 mA cm⁻², V_oc = 0.64 V, and ff = 0.68) under 100 mW cm⁻² simulated AM 1.5 G solar irradiation.     

A natural tomato slurry as a photosensitizer for dye-sensitized solar cells with TiO2/CuO composite thin films

We have studied the performance of dye-sensitized solar cells by employing natural dye “anthocyanins” extracted from the tomato slurry as a sensitizer for the TiO₂/CuO photoanode. The extracts were anchored on TiO₂/CuO films deposited on an ITO substrate which was used as a photoanode. The dye adsorbed TiO₂/CuO films electrode, the copper plate as a counter electrode, and iodolyte as an electrolyte were assembled into DSSCs. The conversion efficiency of the DSSCs was found to be 2.96% with a V_OC of 0.615 V, J_SC of 6.6 mA/cm², and an FF of 0.73. This work highlights the use of contribution of the tomato slurry as a natural sensitizer to enhance the efficiency of DSSCs.     

Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells

Four porphyrin dyes, incorporating multi-alkylthienyl appended porphyrins as the electron donor, the 2-cyanoacrylic acid as the electron acceptor, and different π-conjugated spacer, have been synthesized for dye-sensitized solar cells (DSSCs). All the porphyrin dyes studied in this work exhibit red-shifted and broadened electronic spectra respect to the reference P_Zn as expected. By the introduction of thienyl groups at the meso-positions, the energy level of E_ox (excited-state oxidation potentials) is significantly shifted to the positive compared with the reference P_Zn, indicating a decreased HOMO-LUMO gap. The highest power conversion efficiency of the four dyes based on DSSCs reached 5.71% under AM 1.5 G irradiation.     

A near-infrared dye for dye-sensitized solar cell: Catecholate-functionalized zinc phthalocyanine

The design and synthesis of an asymmetrical zinc phthalocyanine sensitizer modified with a catechol anchoring group is reported. The performance of this sensitizer was evaluated in a dye-sensitized solar cell. A strong interaction between the catechol dye and TiO₂ (with the formation of a five-membered charge-transfer complex) was evidenced by a strong shift in the Q-band of the ZnPc-Cat from 680 nm in solution to 750 nm on TiO₂, along with an appreciable absorption tail extending to ∼1000 nm. The fabricated solar cell containing the phthalocyanine sensitizer showed relatively high light-to-electron conversion efficiency (η = 0.92%), considering that few catechol dyes exceed η = 0.7% in dye-sensitized solar cells. Values of I_sc = 2.53 mA cm⁻² and V_oc = 540 mV were obtained, referring to a standard N719 cell (η = 6.46%). A comparison of zinc phthalocyanine sensitizers bearing different anchoring groups affirmed the superiority of carboxylate groups relative to those bearing catechol groups in terms of cell performance.     

Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells

This study employed a solution-based method to prepare a 3-D hybrid material comprising graphene and acid-treated multi-walled carbon nanotubes (MWCNTs). The adsorption of MWCNTs on graphene reduces the π–π interaction between graphene sheets resulting from steric hindrance, providing a subsequent reduction in aggregation. Optimal proportions of MWCNTs to graphene (2:1) enabled the even distribution of individual MWCNTs deposited on the surface of the graphene. The hybrid 3-D material was incorporated within a TiO₂ matrix and used as a working electrode in dye-sensitized solar cells (DSSCs). The hybrid material provides a number of advantages over electrodes formed of either MWCNTs or graphene alone, including a greater degree of dye adsorption and lower levels of charge recombination. In this study, DSSCs incorporating 3-D structured hybrid materials demonstrated a conversion efficiency of 6.11%, which is 31% higher than that of conventional TiO₂-based devices.     

Conversion enhancement of flexible dye-sensitized solar cells based on TiO2 nanotube arrays with TiO2 nanoparticles by electrophoretic deposition

We prepared highly ordered titanium dioxide nanotube arrays (TNAs) by anodizing Ti foils in F⁻ containing electrolyte. The thickness and dye loading amount of TNAs were 26 μm and 1.06 × 10⁻⁷ mol cm⁻², respectively. TiO₂ nanoparticles (TNPs) were electrophoretically deposited on the inner wall of nanotube to produce coated nanotube arrays (TNAP). The dye loading was increased to 1.56 × 10⁻⁷ mol cm⁻², and the electron transport rate improved. TNAs and TNAP were sensitized with ruthenium dye N3 to yield dye-sensitized TiO₂ nanotube solar cells. The power conversion efficiency of TNA-based dye-sensitized solar cells (DSSCs) was 4.28%, whereas the efficiency of TNAP-based DSSCs increased to 6.28% when illuminated from the counter electrode. The increase of power conversion efficiency of TNAP-based DSSCs is ascribed to the increased surface area of TNAs and the faster electron transport rate.     

Novel D-π-A system based on zinc porphyrin dyes for dye-sensitized solar cells: Synthesis, electrochemical, and photovoltaic properties

We have designed and synthesized novel zinc porphyrin dyes which have a D-π-A system based on porphyrin derivatives containing a triphenylamine (TPA) electron-donating group and a phenyl carboxyl anchoring group substituted at the meso position of the porphyrin ring, yielding the push-pull porphyrins as the most efficient green dye for dye-sensitized solar cell (DSSC) applications. The synthesis and characterization of a novel D-π-A system based on zinc-porphyrin derivatives have been investigated through their photophysical and photoelectrochemical studies. A large red-shift of the absorption maxima due to introduction of the TPA moiety at the meso position of the porphyrin ring was expected in the D-π-A porphyrins, but the absorption maxima of HKK-Por dyes were a little red-shifted in contrast to Zn[5,-10,15-triphenyl-20-(4-carboxylphenyl)-porphyrin], due to the tilted structure between TPA and the porphyrin unit. Under the photovoltaic performance measurement, the maximum incident photon-to-current conversion efficiency (IPCE) value of the DSSC based on HKK-Por 5 was slightly higher than the efficiencies of the DSSCs based on other HKK-Por dyes due to the introduction of the alkoxy group into the TPA moiety at the meso position of the porphyrin ring. A maximum photon-to-electron conversion efficiency of 3.36% was achieved with the DSSC based on HKK-Por 5 dye (J_SC = 9.04 mA/cm², V_OC = 0.57 V, FF = 0.66) under AM1.5 irradiation (100 m Wcm⁻²).     

Solid‐state dye‐sensitized and bulk heterojunction solar cells using TiO2 and ZnO nanostructures: recent progress and new concepts at the borderline

In the field of photovoltaic energy conversion, hybrid inorganic/organic devices represent promising alternatives to standard photovoltaic systems in terms of exploiting the specific features of both organic semiconductors and inorganic nanomaterials. Two main categories of hybrid solar cells coexist today, both of which make much use of metal oxide nanostructures based on titanium dioxide (TiO₂) and zinc oxide (ZnO) as electron transporters. These metal oxides are cheap to synthesise, are non‐toxic, are biocompatible and have suitable charge transport properties, all these features being necessary to demonstrate highly efficient solar cells at low cost. Historically, the first hybrid approach developed was the dye‐sensitized solar cell (DSSC) concept based on a nanostructured porous metal oxide electrode sensitized by a molecular dye. In particular, solid‐state hybrid DSSCs, which reduce the complexity of cell assembly, demonstrate very promising performance today. The second hybrid approach exploits the bulk heterojunction (BHJ) concept, where conjugated polymer/metal oxide interfaces are used to generate photocurrent. In this context, we review the recent progress and new concepts in the field of hybrid solid‐state DSSC and BHJ solar cells based on TiO₂ and ZnO nanostructures, incorporating dyes and conjugated polymers. We point out the specificities in common hybrid device structures and give an overview on new concepts, which couple and exploit the main advantages of both DSSC and BHJ approaches. In particular, we show that there is a trend of convergence between both DSSC and BHJ approaches into mixed concepts at the borderline which may allow in the near future the development of hybrid devices for competitive photovoltaic energy conversion. Copyright © 2011 Society of Chemical Industry     

Effect of an Nb2O5 nanolayer coating on ZnO electrodes in dye-sensitized solar cells

Nanostructured porous zinc oxide electrodes for use in dye-sensitized solar cells (DSSCs) were coated with thin niobium oxide layers by using sol–gel transformation of niobium pentaethoxide in air. Coating solutions were prepared by mixing niobium pentaethoxide and ethanol. A dip-coating technique was adopted at a low withdrawal speed of 100 μm s⁻¹. The coated electrodes were then heat-treated at temperatures between 400 and 600 °C. The presence of niobium in the coated electrodes was confirmed by X-ray photoelectron spectroscopy. As expected, the niobium oxide layers worked as an energy barrier between the ZnO electrode and electrolyte. Open-circuit voltage (V_OC) of the cells using the coated electrodes was then enhanced up to 0.768 V, which was attributable to the suppression of the recombination of photogenerated electrons with oxidized species in electrolytes. An additional benefit of the coating was that grain growth of ZnO particles in the electrodes was hindered and short-circuit photocurrent density (J_SC) was kept relatively high due to large amounts of adsorbed dye. An overall light-to-electricity conversion efficiency was increased to a maximum of 5.19%, indicating that the proper coating technique was the key for improving the performance of ZnO-based DSSCs.     

Carbazole based hole transporting materials for solid state dye sensitizer solar cells: role of the methoxy groups

The synthesis of new organic hole transporting materials (HTMs) based on 3,6‐disubstituted 9H‐carbazole‐3,6‐diamine,N,N,N′,N′‐tetraphenyl‐9‐(4‐methoxyphenyl) derivatives and their applications in solid state dye sensitizer solar cells (DSSCs) are described. The effect of the methoxy group localized on the para position of the diphenylamine moieties on the thermal, electronic and electrochemical properties and photovoltaic performance is discussed. In solid state DSSCs, utilization of the aforementioned HTMs in combination with the dye D102 (TiO₂/D102/HTM/Au) shows a positive influence of the methoxy group on the photovoltaic conversion efficiency compared with unsubstituted diphenylamine grafted groups. A study on the concentration of the HTM is also carried out and shows an optimal concentration around 200 mg mL^?1. Without further optimization, the best device gives a power conversion efficiency of 1.75% under AM 1.5 solar irradiation (100 mW cm^?2).