Mesoporous F-doped ZnO prism arrays with significantly enhanced photovoltaic performance for dye-sensitized solar cells

A photoanode with a mesoporous F-doped ZnO prism array (F-ZnO PA) is prepared on an F-SnO₂ (FTO) glass substrate and its application in a dye-sensitized solar cell (DSSC) is investigated. A superstructure of mesoporous F-ZnO PA is obtained by thermal treatment of ZnF(OH) PA precursor, which has been previously grown directly onto the FTO substrate via chemical bath deposition. The structure and morphology of the films are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and TEM-EDS elemental mapping. The ZnO prisms are homogenously doped by F and composed of oriented nanograins and nanopores. Owing to the higher surface area and stronger light scattering, as well as longer electron lifetime and lower charge-transfer resistance, an electrical energy conversion efficiency (η) of 3.43% is achieved for a DSSC containing a 5 μm thick mesoporous F-ZnO PA photoanode, which is much higher than that for a similar cell based on a ZnO nanorod photoanode. The knowledge acquired in this work is important for the design of efficient photoanode materials for DSSCs.     

Anthraquinone dyes as photosensitizers for dye-sensitized solar cells

Three anthraquinone dyes with carboxylic acid as anchoring group are designed and synthesized as sensitizers for dye-sensitized solar cells (DSSCs). Preliminary photophysical and photoelectrochemical measurements show that these anthraquinone dyes have very low performance on DSSC applications, although they have broad and intense absorption spectra in the visible region (up to 800 nm). Transient absorption kinetics, fluorescence lifetime measurements and density functional theory (DFT) calculations are conducted to investigate the cause of such low DSSC performance for these dyes. The results show that the strong electron-withdrawing character of the two carbonyl groups on anthraquinone framework may lie behind the low performance by suppressing the efficient electron injection from the dye to the conduction band of TiO₂.     

Preparation of transparent and conducting boron-doped ZnO electrode for its application in dye-sensitized solar cells

A simple and economic chemical spray pyrolysis method is used to prepare transparent and conducting boron-doped zinc oxide (B_nZnO) electrode having potential applications in dye-sensitized solar cells (DSSCs). The B_nZnO electrodes were critically characterized for their structural, morphological and electrical properties. The B_nZnO electrode with 2 at% boron doping showed average grain size of 20(±1) nm, surface roughness of 9 nm, ?95% transparency and resistivity of 4.5×10⁻³ Ω cm⁻¹. Furthermore, doping concentration of boron could also be easily controlled for achieving desired properties. Using this electrode as a substrate in DSSCs, the solar-to-electrical conversion efficiency with N3 dye as a sensitizer was noted to be 1.53%. This work suggests that the B_nZnO electrodes could be used as promising alternative to presently used indium- or fluorine-doped tin oxide as substrates.     

Improvement of the performance of dye-sensitized solar cells using Sn-doped ZnO nanoparticles

Sn-doped and undoped ZnO nanoparticles were synthesized by hydrothermal method and their performance as the photoanode of dye-sensitized solar cells (DSSCs) was investigated. Energy dispersive X-ray spectroscopy and X-ray diffraction showed that the Sn had been doped into the ZnO lattice. A red shift of photoluminescence spectra which was induced by Sn doping was observed. The photocurrent density-voltage curves of DSSCs indicated that the efficiency was increased by as high as 140% on bare-FTO substrate and 105% on ZnO compact layer/FTO substrate via Sn doping. Also the effect of the ZnO compact layer was discussed by both of Sn-doped or undoped DSSCs.     

Synthesis of nanocrystalline ZnO powder via sol-gel route for dye-sensitized solar cells

This paper reports the growth mechanism of sol-gel-derived nanocrystalline ZnO powder. The influence of pH value of the sol on the crystallite size, morphology and structure of ZnO powder was investigated by using X-ray diffraction, transmission and scanning electron microscopy. Maximum size nanocrystallite (∼14 nm) of ZnO powder was obtained for pH value of 9. An increase in the band gap (blue shift) was observed with decrease in the size of the ZnO nanocrystallites. The variation in band gap was found to be in agreement with theoretical calculations using effective mass model. The growth mechanism of ZnO particles from zinc acetate dihydrate precursor by the sol-gel process has been discussed in terms of solvation, hydrolysis and polymerization. The synthesized ZnO powders were successfully used as the electrode material for dye-sensitized solar cells.     

A novel approach to titania nanowire arrays as photoanodes of back-illuminated dye-sensitized solar cells

Titania nanowire arrays have been deposited on Ti foils through direct oxidizing the Ti substrate with aqueous hydrogen peroxide solutions containing melamine and nitric acid, and the applicability of such nanowire arrays to back-illuminated dye-sensitized solar cells studied in parallel with titania nanotube arrays on Ti foils. The low-temperature nitrogen adsorption measurement reveals that the film with nanowires 25 nm in diameter and 1 μm in length possesses a BET specific surface area of 59.0 m² g⁻¹, a value much larger than 26 m² g⁻¹ calculated for the nanotube with an inner diameter of 80 nm, an outer diameter of 120 nm and a total length of 3 μm. Assuming an indirect transition between band gaps, the nanowire film exhibits a bandgap of 3.1 eV, slightly larger than that of 3.0 eV for the nanotube one. A detailed electrochemical study suggests that, in comparison with the nanotube film, the nanowire one exhibits much lower saturated photocurrent and poorer conductivity under the Xe-lamp irradiation. However, when utilized to construct back-side illuminated dye-sensitized solar cells, the cell with the 2 μm-thick nanowire photoanode possesses significantly higher efficiency than the one with the 3 μm-thick nanotube photoanode. The relatively high energy conversion efficiency is contributed to the high specific surface area and the unique mesoporous structure of the titania nanowire arrays, which favors the adsorption of dye molecules.     

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.     

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.     

A study of stainless steel-based dye-sensitized solar cells and modules

Stainless steel (StSt) has been applied as substrate material for efficient, flexible, nanoporous TiO₂ dye-sensitized solar cells (DSSCs) with the aim of improving the photochemical properties of current plastic-based flexible DSSCs. DSSCs with a StSt substrate show almost equivalent properties in efficiency and convenience to cells with a F-doped tin oxide (FTO) glass substrate. Specifically, the metal substrate allows application of high-temperature sintering processes and shows high conductance even after sintering. Cells fabricated with the StSt substrates have been investigated as individual cells and as modules. A comparison between conventional DSSCs with a FTO glass substrate and flexible DSSCs with a StSt substrate is presented. In addition, Pt-coated electrodes, which can serve as window electrodes for StSt-based DSSCs, are fabricated via two different methods, i.e., chemical reduction and annealing, and compared.     

Effects of annealing conditions on the photoelectrochemical properties of dye-sensitized solar cells made with ZnO nanoparticles

Dye-sensitized solar cells (DSSCs) were fabricated by using porous ZnO electrodes derived from home-made ZnO nanoparticles. Electrochemical impedance spectra and open-circuit photovoltage decay curves measurements were performed to investigate the photoelectrochemical characteristics of ZnO films annealed at different temperatures. The experimental results indicate that the effects of the bulk traps and the surface states within the ZnO films on the recombination processes of the photoinjected electrons in DSSCs depend on the annealing temperature. The DSSC based on the ZnO electrode annealed at 400 °C exhibits an optimal energy conversion efficiency of 3.92% under the illumination of one sun simulated sunlight because the farthest decrease in the effects of both bulk traps and surface states at this film can maintain a lower charge recombination probability. This result indicates that the ZnO film electrode has promising application in the field of DSSCs, and the optimization of porous film fabrication condition is efficient for the improvement of ZnO-based DSSC’s performances.     

Carbon-nanofiber counter electrodes for quasi-solid state dye-sensitized solar cells

Carbon-nanofibers (CNFs) with antler and herringbone structures are studied as a tri-iodide (I₃⁻) reduction electrocatalyst in combination with the liquid electrolyte or an alternative stable quasi-solid state electrolyte. The catalytic properties of the counter electrode (CE) are characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The doctor bladed low temperature CNFs-CE has faster I₃⁻ reduction rate and low charge transfer resistance (R_CT) of ∼0.5 Ω cm² than platinum (Pt) (∼2.3 Ω cm²) due to the nanofiber stacking morphology. Its herringbone and antler structures with graphitic layers lead to defect rich edge planes and larger diameter of CNFs facilitate the electron transfer kinetics. The cells with CNF counter electrodes are showing promising energy conversion efficiency greater than 7.0% for the glass based devices and 5.0% for the flexible cells filled with the quasi-solid state electrolyte, which is similar to Pt performance. Application of CNFs-CE in flexible and quasi-solid state electrolyte increases the possibility of roll to roll process, low cost and stable dye-sensitized solar cells (DSCs).     

Optical properties of nano-structured dye-sensitized solar cells

Radiative transfer computations are carried out to describe the intrinsic and effective optical properties of light diffusing and absorbing materials consisting of anatase titania pigments hosted in an electrolyte medium. The intrinsic visible absorption of some of the pigments has been increased by coating them with an absorbing dye monolayer. A multiple scattering approach is applied to compute average path-length parameters and forward-scattering ratios used in four-flux radiative transfer calculations. It is shown that the effective absorption coefficient of the inhomogeneous medium is maximized when the size of the pigments is around 12 nm in diameter, and the effective scattering coefficient is optimized for diameters of the pigments around 250 nm. The intrinsic solar absorptance of the medium is optimized when the diameter of the pigments is around 60 nm.     

Faradaic impedance of dye-sensitized solar cells

Theoretical equations of the Faradaic impedance of the photoelectrode and the counter electrode of dye-sensitized solar cell (DSC) were derived. The Faradaic impedance is the frequency dependent resistance related to the time constants of elementary electrode processes like photoexcitation, electron transfer, charge transfer reaction and diffusion. The typical cell impedance spectrum describes the locus of three semicircles on the Nyquist plane. The locus of three semicircles is generally analyzed by using the equivalent circuit composed of charge transfer resistance (R_ct,1) and capacitance (C_dl,1) of counter electrode, charge transfer resistance (R_ct,2) and capacitance (C_dl,2) of photoelectrode, the finite diffusion impedance due to the diffusion of I₃⁻ on the counter electrode (Z_w), and total resistance of the substrate and solution (R_s). The physical meanings of R_ct,1 and R_ct,2 can be elucidated by the interpretations of Faradaic impedance derived in the present paper. The R_ct,1 is represented as the function of the potential-dependent rate constants of I₃⁻ reduction and I⁻ oxidation. On the other hand, the R_ct,2 is the function of the photoelectrode potential, the surface concentration of I₃⁻ and the potential-independent rate constant of the back electron transfer reaction. The theoretical expressions of the current-voltage (I-V) curve of the DSC can be also derived. In the present paper, the relations between the impedance and I-V curve of the DSC are discussed.     

Utilization of natural carotenoids as photosensitizers for dye-sensitized solar cells

The dye-sensitized solar cells (DSCs) were assembled by using natural carotenoids, crocetin (8,8′-diapocarotenedioic acid) and crocin (crocetin-di-gentiobioside), as sensitizers and their photoelectrochemical properties were investigated taking a presence or absence of carboxylic group in the dye molecule into consideration. In these carotenoids, crocetin that has carboxylic groups in the molecule can attach effectively to the surface of TiO₂ film so that it performed the best photosensitized effect resulting in the short-circuit photocurrent with 2.84 mA under irradiation of 1.0 cm². On the other hand, crocin that has no carboxylic group in the molecule showed lower photoelectrochemical performance because of its lower affinity to the surface of TiO₂ film. These results indicate that it is possible to apply carotenoid as sensitizers for DSCs at the presence of effective function groups.     

Low-Pt-loading acetylene-black cathode for high-efficient dye-sensitized solar cells

We reported on the synthesis, characterization, and photovoltaic/electrochemical properties of Pt/acetylene-black (AB) cathode as well as their application in dye-sensitized solar cells (DSCs). The Pt/AB electrode was prepared through a thermal decomposition of H₂PtCl₆ on the AB substrate. SEM and TEM observations showed that the Pt nanoparticles were homogeneously dispersed on the AB surface. The Pt-loading content in the Pt/AB electrode was only about 2.0 μg cm⁻², which was much lower than 5–10 μg cm⁻² generally used for the Pt electrode in DSCs. Electrochemical measurements displayed a low charge-transfer resistance of 1.48 Ω cm² for the Pt/AB electrode. Furthermore, when this low-Pt-loading electrode was used as the cathode of DSCs, an overall light-to-electricity energy conversion efficiency of 8.6% was achieved, showing commercially realistic energy conversion efficiency in the application of DSCs.     

Dye-sensitized solar cells based on semiconductor morphologies with ZnO nanowires

ZnO nanowires and structures that combine nanowires and nanoparticles were used as the wide band gap semiconducting photoelectrode in dye-sensitized solar cells (DSSCs). The nanowires provide a direct path from the point of photogeneration to the conducting substrate and offer alternative semiconductor network morphologies to those possible with sintered nanoparticles. Growing nanowires with dendrite-like branched structure greatly enhances their surface area, leading to improved light harvesting and overall efficiencies. Hybrid cells based on a combination of nanowires and nanoparticles can be tailored to take advantage of both the high surface area provided by the nanoparticles and the improved electron transport along a nanowire network. Solar cells made from branched nanowires showed photocurrents of 1.6 mA/cm², internal quantum efficiencies of 70%, and overall efficiencies of 0.5%. Solar cells made from appropriate hybrid morphologies show photocurrents of 3 mA/cm² and overall efficiencies of 1.1%, while both the nanowire and hybrid cells show larger open circuit voltages than nanoparticle cells.     

Application of mesoporous carbon to counter electrode for dye-sensitized solar cells

The mesoporous carbons were prepared by the carbonation of the triblock copolymer F127/phloroglucinol-formaldehyde composite self-assembled in an acid medium and employed as the catalyst for triiodide reduction in dye-sensitized solar cells (DSCs). The characteristics of mesoporous carbon were analyzed by scanning electron microscopy, transmission electron microscopy, N₂ sorption measurement and X-ray diffraction. The mesoporous carbon with low crystallinity exhibited Brunauer-Emmett-Teller surface area of 400 m² g⁻¹, pore diameter of 6.8 nm and pore volume of 0.63 cm³ g⁻¹. The photovoltaic performances of DSCs with mesoporous carbon counter electrode were improved by increasing the carbon loading on counter electrode due to the charge-transfer resistance of mesoporous carbon counter electrode decreasing with the increase of the carbon loading. However, further carbon loading increase has no obvious effect on the photovoltaic performance of DSCs with carbon electrode when carbon loading exceeds 300 μg cm⁻². The overall conversion efficiency of 6.18% was obtained by DSCs composed of mesoporous carbon counter electrode with the carbon loading of 339 μg cm⁻². This value is comparable to that of DSCs with conventional platinum counter electrode.     

A novel UV-mediated low-temperature sintering of TiO2 for dye-sensitized solar cells

Titania pastes were fired at 450 °C in oxygen to give white titania that was used to prepare dye-sensitized solar cells (DSSC). Titania fired at lower temperature and/or under inert atmosphere have brown stripes and cells made from these stripes had no measurable efficiency. When the titania paste was screen printed and then heated and simultaneously irradiated with UV light, white stripes were obtained. Improved efficiency was noted for PV cells made from pastes heated at lower temperature under irradiation vs. cells made from low-temperature heated paste but without irradiation. UV irradiation appears to facilitate clean oxidation of residual organic materials in the titania precursor pastes. The best cells in our study made with our titania paste treated at 450 °C in oxygen had the following characteristics: efficiency=3.45%; V_oc=630 mV; J_sc=8.5 mA/cm²; and a fill factor=0.64.     

Synthesis and characterization of ZnO nanowires grown on different seed layers: The application for dye-sensitized solar cells

Zinc oxide (ZnO) nanowire electrodes which were grown on different seed layers and examination of their significant effects on the performance of dye sensitized solar cells were studied. Through chemical bath deposition process, the ZnO nanowires were grown on an indium tin oxide (ITO) coated glass using sputter-deposited aluminum doped zinc oxide (AZO) and ZnO seed layers. Afterward, main parameters such as solution concentration, growth temperature, and time were systematically investigated based on morphology of nanowires. The X-ray diffraction (XRD), field emission scanning microscopy (FESEM), and photoluminescence (PL) were applied to investigate the characteristics of the samples. The results showed ZnO nanowires, which were grown by AZO seed layer, had a high density array with hexagonal wurtzite structure distributed vertically and uniformly on ITO coated glass. The mentioned zinc-oxide nanowires grown under an optimum condition on different seed layer were used to fabricate dye solar cells afterward. The seed layer was effective on morphologic, optical, and structural features. The overall light-conversion efficiency of dye sensitized solar cell with ZnO nanowires grown on AZO seed layer was almost 2 times higher than that of those grown on ZnO seed layer. Electrochemical impedance spectroscopy analysis was measured under standard light to investigate the electron transport properties in the both ZnO-NW DSSCs. As the results showed, photoanode electron recombination rate with electrolyte was 6.02 Hz for dye solar cells of zinc oxide (ZnO-NWDSSC) produced by ZnO seed layer, which is 2.5 times faster than cells with AZO seed layer.     

Reaction between oxide sealant and liquid electrolyte in dye-sensitized solar cells

The iodide and tri-iodide reduction-oxidation couples in the liquid electrolyte of dye-sensitized solar cells (DSSCs) are very reactive and corrosive with the other components of the DSSCs, especially the sealing material. A leakage of the liquid electrolyte to cells generally occurs in the DSSCs because of a chemical reaction between the sealing material and the electrolyte. This leakage is correlated to the long-term stability and energy conversion efficiency of the dye-sensitized solar module. This study examined the reactions between the electrolyte and the glass using a leaching test with the aim of using this material as the matrix of the sealing materials in DSSCs. The prepared samples were evaluated using an inductively coupled plasma spectroscope, a nanoindentation test, an atomic force microscope and a contact angle analyzer. After the leaching test, the zinc and boron ions from the glass were leached into the electrolyte after immersion for 1 h. The elastic modulus, hardness, and surface roughness of the glass changed after the formation of the leached layer of the glass surface. The results suggested that the compositions of the oxide sealant should be considered in terms of the chemical stability in the electrolyte.