Photoaction, temperature and O2 depletion effects in fullerene photoelectrochemical solar cells

It is demonstrated that higher temperature and C₆₀ oxygen depletion increase the photocurrent of fullerene photoelectrochemical solar cells (PEC). Fullerene/iodide electrolyte PEC consisting of intrinsic single crystal C₆₀ in either aqueous 3 M KI, 0.01 M I₂, or 0.1 M tetrabutyl ammonium iodide, 0.3 M LiClO₄ in acetonitrile solution, drive regenerative photoinduced iodide oxidation. The photocurrent is increased by an order of magnitude (to 6.4 μA/cm² under 100 mW/cm² illumination) by an increase of the aqueous cell temperature from 24°C to 82°C. A similar order of magnitude increase in photocurrent is accomplished by O₂ depletion pretreatment (24 h at 400°C in Ar) of the C₆₀ to improve conductivity. However, this latter treatment also irreversibly increases the cell dark current. The spectral action of single crystal C₆₀ is also probed, through the generated photoelectrochemical current in iodide, ferricyanide and sulfuric electrolytes as a function of wavelength. Band edges are observed at 720 nm (1.7 eV) and 560 nm (2.2 eV), and a substantial peak photocurrent response occurs at 395 nm (3.1 eV) and decreases at shorter wavelengths.     

First-principles study of hydrogen storage on Si atoms decorated C60

Hydrogen storage capacity of Si_nC₆₀ is studied via first-principles theory based on DFT and Canonical Monte Carlo Simulation (CMCS). It is shown that Si atoms strongly prefer D-site rather than other sites and in these structures maximum number of hydrogen molecule onto any Si atom is one. Each Si atom adsorbs one hydrogen molecule in molecular form and with proper binding energies when Si atom is placed in any D-site of C₆₀. Si atoms enhance remarkably hydrogen storage capability in fullerene.     

Photoelectron spectroscopy and atomic force microscopy study of 1,2-dicyano-methanofullerene C60(CN)2 thin film for photovoltaic applications

1, 2-dicyano-methanofullerene (C₆₀(CN)₂) is a soluble fullerene derivative that has been reported to have stronger electron affinity than parent C₆₀. Ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) experiments were carried out on C₆₀(CN)₂ thin films spin coated on heavily doped n-type Si substrate. UPS spectra enabled the determination of the vacuum shift at the fullerene derivative/Si interface and the onset of the highest occupied molecular orbital (HOMO). From the UV-vis absorption spectra of C₆₀(CN)₂ thin films spin coated on quartz substrates, the optical band gap (E_g) and the onset of absorption were determined. These measurements allowed the determination of the lowest occupied molecular orbital (LUMO) position. The morphology of the deposited film was probed by AFM and reveals non-uniformity of the thin film. Open circuit voltage (V_oc) measurements on P3HT/C₆₀(CN)₂ based organic solar cell device are compared to the commonly used P3HT/PCBM device.     

Molecular films based on polythiophene and fullerol: theoretical and experimental studies

We report the electrical and optical properties of molecular films made of homogeneous and segregated mixtures of polythiophene with both C₆₀ and C₆₀(OH)_24–28 compounds, and relate the trends observed with theoretical predictions based on systematic studies of the electronic structure and energetics of polyhydroxylated fullerenes. The electric and optical properties are strongly correlated to the degree of phase segregation in the molecular films and also to the tendency of the hydroxyl groups to cluster on the C₆₀ cage, thus providing useful information on the potential of hydroxylated fullerenes for the development of buffer layers for fullerene/conductive polymer solar cells. Finally, we underline the importance of quantifying the changes in the electronic structure of the C₆₀ molecules when the chemical functionalization of their surfaces is performed in order to better understand and improve the efficiency of fullerene-based solar cell materials.     

Mg@C60 nano-lamellae and its 12.50 wt% hydrogen storage capacity

The design and synthesis of new hydrogen storage materials with high capacity are the prerequisite for extensive hydrogen energy application which can be achieved by multi-site hydrogen storage. Herein, a Mg@C₆₀ nano-lamellae structure with multiple hydrogen storage sites has been prepared through a simple ball-milling process in which Mg nanoparticles (∼5 nm) are homogeneously dispersed on C₆₀ nano-lamellae. The as-obtained C₆₀/Mg nano-lamellae displays an excess hydrogen uptake of 12.50 wt% at 45 bar, which is far higher than the theoretical value (7.60 wt%) of metal Mg and the US Department of Energy (DOE) target (5.50 wt%, 2020 year), also the experimental values reported by now. The enhanced hydrogen storage mainly comes from several storage sites: MgH₂, H_x–C₆₀ (CH chemical bonding), H₂@C₆₀ (the endohedral H₂ in C₆₀). Interestingly, the hybridization of Mg and C₆₀ not only facilitate the dissociation of H₂ molecules to form CH bonding with C₆₀, but also promote the deformation of C₆₀ and access H₂ molecules into the cavity of C₆₀. This work provides new insight into the underlying chemistry behind the high hydrogen storage capacities of a new class of hydrogen storage materials, fullerene/alkaline-earth metals nanocomposites.     

Improved n-Si/oxide junctions for environmentally safe solar energy conversion

The considerable interest in the practical use of solar energy has increased the importance of photovoltaic and photoelectrochemical systems. Metal oxide films like tin dioxide (SnO₂), titanium oxide (TiO₂) or indium tin oxide (ITO) are known to form stable photovoltaic junction with semiconductors of practical relevance like silicon (Si). Thin films of SnO₂ and TiO₂ were prepared easily and conveniently on the surface of silicon wafers by the spray pyrolysis technique. The prepared heterojunctions, i.e. the Si/oxide junction represent the main part of stable and efficient solar energy converter. In these systems, the solid/solid junction (n-Si/oxide) is separated from the site of the environmental interaction by the stable oxide film (SnO₂ or TiO₂) that protect the conventional semiconductor from photocorrosion.Besides its use in the fabrication of photovoltaic cells, the n-Si/oxide was used in the preparation of photoelectrochemical cells. The characteristics of the oxide film were subjected to a series of improvements either in the surface conductivity or the band gap energy, i.e. the position of the Fermi level of the semiconducting oxide by incorporating foreign atoms in the oxide film matrix during its preparation. The incorporation of Ru in the thin oxide film leads to the improvement of the solar conversion efficiency by improving the fill factor of the photovoltaic or photoelectrochemical cells. Such improvement enables the use of the prepared cells as clean energy converters. The fabricated solar cells have an average open-circuit potential of 0.44–0.62 V and a short circuit current of 28–30 mA/cm². A conversion efficiency up to 14% was achieved.     

Higher fullerenes as electron acceptors for polymer solar cells: A quantum chemical study

In the present study, we have used quantum chemical methods to study the energy levels of the frontier orbitals of higher fullerene derivatives (from C₇₀ to C₈₄ and having the same addend as in [6,6]-phenyl C₆₁-butyric acid methyl ester) with the aim to understand if they can be used as electron acceptors in bulk heterojunction polymer–fullerene solar cells. Higher fullerenes have a stronger and broader absorption compared to C₆₀ and they can improve the current output of the corresponding devices. The geometries of all the compounds were optimized with the density functional theory at the B3LYP/3-21G* level of calculation. The lowest unoccupied molecular orbital (LUMO) levels of the investigated compounds correlate well with the reduction potentials (obtained by cyclic voltammetry) of the already prepared species. We found that the LUMO level depends not only on the fullerene size (number of carbons of the cage) and constitutional isomer, but also on the position and, in some cases, the addend orientation. This issue should be considered because for a proper device operation, a well-defined LUMO is required. The position of the LUMO level of some higher fullerene derivatives can be suitable for low-bandgap polymers.     

Progress in stability of organic solar cells exposed to air

In this paper, the stability of small-molecule organic solar cells based on copper phthalocyanine (CuPc) and fullerene (C₆₀) is investigated. The use of silver instead of aluminum as the metal electrode in these solar cells, with smaller grain size and grain boundaries as well as with more uniform grain size distribution in the film, results in significant improvement in the lifetime of the devices. The substantial role of silver in the protection of the cells against permeation of oxygen and/or water molecules into the organic thin films is confirmed. Substitution of a thin buffer layer (70 Å) of bathophenanthroline (Bphen) for bathocuproine (BCP), sandwiched between C₆₀ and the cathode, makes considerable progress in the lifetime of the device.     

Organic donor, acceptor and buffer layers of small molecules prepared by OVPD technique for photovoltaics

Organic vapour-phase deposition (OVPD^®) is used for the growth of the organic solar cell component materials such as the donor copper phthalocyanine (CuPc), the acceptor fullerene C₆₀, and electron-conducting buffer layers of bathocuproine (BCP) on Si1 0 0 wafers and indium tin oxide (ITO) substrates on areas as large as 15×15 cm². By means of X-ray diffraction (XRD) analysis we show that under continuous operating conditions the source materials possess long-term stability. The CuPc, C₆₀ and BCP thin film morphology and structure are characterised using scanning electron microscopy and XRD analysis. We demonstrate CuPc thin films with a highly folded surface morphology suitable for the preparation of solar cells with an interpenetrating donor–acceptor interface. The XRD diffraction patterns of the CuPc and C₆₀ layers deposited under conditions appropriate for the preparation of organic solar cells show spectra typical for these materials. Mixed CuPc:C₆₀ layers with controlled constituent ratios and layer thickness are deposited for the preparation of organic solar cells. First ITO/CuPc:C₆₀/Al organic photovoltaic devices are prepared with an efficiency of 1% (conditions AM1.5).     

Improving power conversion efficiency in polythiophene/fullerene-based bulk heterojunction solar cells

In the present work, we have studied photovoltaic devices fabricated from a blend of regioregular poly (3-hexlthiophene) (P3HT) and Buckminster fullerene. The solvent and composite ratio have been selected to obtain best morphology and minimum degradation. Buffer layers of poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) (PEDOT:PSS) at the anode and of LiF at the cathode were used to improve the device performance. It was further found that post-annealing of the devices for an optimum duration and temperature improves the solar cells, and the power conversion efficiency of the devices increases to 2.1% at AM1.5. Though the efficiency using [6,6]-phenyl C60 butyric acid methyl ester (PCBM) as the composite acceptor instead of C₆₀ can be higher, it was not used because of its very high cost as compared to C₆₀.     

Hybrid inverted organic photovoltaic cells based on nanoporous TiO2 films and organic small molecules

Solar cells based on nanoporous TiO₂ films with an inverted structure of indium tin oxide (ITO)/TiO₂/copper phthalocyanine (CuPc):fullerene (C₆₀)/CuPc/poly(3,4-oxyethyleneoxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/Au were fabricated. The best overall photovoltaic performance undergoing a series of device optimization was achieved with the device of ITO/dense TiO₂ (30 nm)/nanoporous TiO₂ (130 nm)/C₆₀:CuPc (1:6 weight) (20 nm)/CuPc (20 nm)/PEDOT:PSS (50 nm)/Au (30 nm). The device using the nanoporous TiO₂ films has better photovoltaic properties compared to those using dense TiO₂ films. Higher photovoltaic performances were obtained by introducing a coevaporated layer of C₆₀:CuPc between TiO₂ and CuPc. The stability of inverted structure was better than that of the normal device, which gives a promising way for fabrication of solar cells with improved stability.     

Modeling the optical absorption within conjugated polymer/fullerene-based bulk-heterojunction organic solar cells

In this paper, we report our results on the modeling of the optical properties of the bulk-heterojunction “plastic solar cells”, consisting of a solid-state blend of the conjugated polymer poly-[2-(3,7-dimethyloctyloxy)-5-methyloxy]-para-phenylene-vinylene and the fullerene C₆₀ derivative 1-(3-methoxycarbonyl) propyl-1-phenyl [6,6]C₆₁. Upon illuminating these cells with the standard AM 1.5 solar spectrum, the short circuit current can be determined for any given internal quantum efficiency as a function of the active layer thickness. In addition, the depth profiles of photoinduced charge generation rates are calculated. Based on the agreement of this modeling with experimentally determined efficiencies of these solar cells, an internal quantum efficiency of about 80% has been estimated.     

Photovoltaic properties of M-phthalocyanine/fullerene organic solar cells

Photovoltaic devices made from M-phthalocyanine and fullerene have been fabricated and characterized by current–voltage response, lateral time-of-flight photoconductivity, UV-visible absorption and scanning electron microscopy. The effect of varying the central moiety on the photovoltaic performance is examined, and demonstrates that the monovalent and divalent phthalocyanines tend to yield higher efficiencies in blended structures, whereas the trivalent and tetravalent phthalocyanines tend to yield higher efficiencies in a bilayer structure. The apparent reason for the disparity is the measured decrease in the hole transport efficiency in trivalent and tetravalent phthalocyanine upon blending with C₆₀. Furthermore, the open circuit voltages of M-phthalocyanine/fullerene solar cells are grouped together according to the valency of the central moiety.     

Photoelectrochemical solar energy conversion based on blend of poly(3-hexylthiophene) and fullerene

A solid-state photoelectrochemical solar energy conversion device based on blend of poly(3-hexylthiophene) (P3HT) and fullerene (C₆₀) has been constructed and characterized. The photoelectrochemical performance parameters of the device were compared with pure P3HT solid-state photoelectrochemical cell. The current–voltage characteristics in the dark and under white light illumination and photocurrent spectra for front- and backside illuminations have been studied. The following device parameters were obtained: an open-circuit voltage of 97.8 mV and a short-circuit current of 7.28 μA/cm² at light intensity of 100 mW/cm²; IPCE% of 0.43% for front side illumination (ITO/PEDOT) and IPCE% of 0.01% for backside illumination (ITO/P3HT:C₆₀). The dependence of the short-circuit current and an open-circuit voltage on the light intensity and time have also been studied.     

Photoelectric properties of BiVO4 thin films deposited on fluorine doped tin oxide substrates by a modified chemical solution deposition process

BiVO₄ films deposited on Fluorine doped tin oxide glass substrates were successfully prepared by a modified chemical solution deposition process. Structure and optical spectrum analysis show that the resultant BiVO₄ films consist entirely of monoclinic scheelite structure and have a narrow band gap of ～2.66 eV. The films were investigated by photoelectrochemical and photovoltaic measurements with regard to hydrogen production and solar energy conversion under visible light. The BiVO₄ photoanodes show significantly higher visible light induced photoelectrochemical performance (～1.1 mA/cm² at 1.0 V vs. Ag/AgCl) than those reported ones, which is very promising for splitting water to H₂ and O₂. A Schottky BiVO₄ solar cell was also investigated for comparison with photoelectrochemical measurements. The correlation between the photoelectrochemical and photovoltaic behavior for BiVO₄ was explained. Our research should provide important support for the applications of BiVO₄ films or its modified forms such as doping and nanocomposite in heterojunction photoelectrochemical cells and solar cells with suitable energy level alignment at the interface.     

Assessing the use of simple dye-sensitized solar cells for drinking water chlorination by communities with limited resources

Dye-sensitized ZnO and TiO₂ photoelectrochemical cells were constructed using recycled waste materials and readily accessible household chemicals to assess whether it would be feasible for low-income communities to utilise solar energy for drinking water chlorination. Prussian Blue sensitized ZnO cells utilising ferro/ferricyanide and iron/copper redox couples for charge transfer produced open circuit potentials of between 0.19 and 0.53 V, and short circuit currents in the range 0.3–1.5 mA cm^?2. Although the power output from these cells was significantly lower than those using the iodide/triiodide redox couple for charge transfer, the significantly lower cost of construction of cells using alternative electrolytes could make these cells accessible to poor communities for producing small amounts of solar electricity for drinking water chlorination.     

Synthesis and characterization of a novel fullerene derivative for use in organic solar cells

A novel fullerene derivative with an N-hexylphenothiazine moiety, PTZ-C_60, was synthesized and characterized. The new synthesized fullerene showed good solubility in common organic solvents such as toluene, chlorobenzene and 1, 2 dichlorobenzene. The synthetic product PTZ-C₆₀ was characterized by ¹H and ¹³C NMR, FT-IR and UV-vis spectroscopy. Photovoltaic devices were fabricated using the new fullerene derivative as the electron acceptor and P3HT as the electron donor. The configuration of the device was as follows: ITO/PEDOT:PSS/active layer/LiF/Al. The weight ratios of the electron donor to the acceptor in the active layer were 1:0.5, 1:0.7, and 1:1. The open-circuit voltage (V_oc) of the fabricated devices was found to be higher than that of devices based on C₆₀ because the LUMO energy level of the new fullerene derivative was higher than that of C₆₀. Further, the power conversion efficiency (PCE) of these devices was observed to be high when annealing was carried out at 150 °C for 5 min and the thickness of the active layer was 80 nm. The maximum V_oc, short-circuit current density, and PCE of the best device were 0.608 V, 4.393 mA/cm², and 1.29%, respectively.     

Ti3C2 MXene nanoparticles modified metal oxide composites for enhanced photoelectrochemical water splitting

MXene, an emerging family of two-dimensional (2-D) material, has shown outstanding electronic properties and promise for the applications on energy storage and conversion. In this paper, Ti₃C₂ MXene nanoparticles were synthesized by a facile solvent exfoliation method and used to construct metal oxide/Ti₃C₂ heterostructures. When these heterostructures were used as photoanodes for photoelectrochemical water splitting, significantly improved photoactivity and stability were achieved. Compared to pristine TiO₂, 6-fold enhanced applied bias photon-to-current efficiency (ABPE) was achieved for TiO₂/Ti₃C₂ heterostructures. According to the electron spin resonance, electrical impedance spectroscopic and Mott-Schottky measurements, the enhanced photoelectrochemical performance was ascribed to the presence of Ti₃C₂ as oxygen evolution cocatalysts and the strong interfacial interactions between metal oxide and Ti₃C₂. Therefore, our research provides a new way to design MXene-based heterostructures for solar energy conversion applications.     

The effect of fullerene doping on photoelectric conversion using titanyl phthalocyanine and a perylene pigment

The effect of fullerene (C₆₀) doping on photoelectric conversion using titanyl phthalocyanine (TiOPc) and a perylene pigment, N, N′-dimethyl-3,4 : 9,10-perylenebis(dicarboximide) (MPCI), was investigated. A new three-layer cell, ITO/MPCI/C₆₀-doped TiOPc/TiOPc/Au, exhibited a higher quantum yield for charge-carrier photogeneration than a two-layer cell without the C₆₀-doped TiOPc layer, ITO/MPCI/TiOPc/Au, upon irradiation with monochromatic light which TiOPc mainly absorbs. The three-layer cell showed a high conversion efficiency of 0.63% for incident white light at an intensity of ca. 100 mW cm⁻².     

A channel flow cell system specifically designed to test the efficiency of redox shuttles in dye sensitized solar cells

The construction and use of a thin layer flow cell test system employing a TiO₂ working electrode, a platinum quasi-reference electrode and the ruthenium dye (H₂-dcbpy)Ru(NCS)₂ (H₂-dcbpy=2,2′-bipyridine-4,4′-dicarboxylic acid) is described. The efficient design enables significant advantages to be gained over presently available procedures for the measurement of photocurrents of dye-sensitized solar cells. The widely used iodide/triiodide redox shuttle system has been investigated over a wide range of conditions. A linear dependence of photocurrent on cation radius was revealed. Under certain conditions, the photocurrent measured in the presence of the Li⁺ cation is five times larger than when the (C₄H₉)₄N⁺ cation is used. Additionally, the addition of low concentrations of cations with small diameters has a significant catalytic enhancement effect on the photocurrent. Other redox shuttles, based on ferrocene, thiocyanate, triiodide and bromide, were tested for their performance in the flow cell and compared to iodide. However, despite some apparent thermodynamic advantages, the photocurrents obtained with these redox shuttles were more than two orders of magnitude lower than those measured with iodide. This finding implies that the efficiency of redox shuttles is limited by kinetic restraints rather than their thermodynamic properties and confirms that the iodide/triiodide system is the dominant redox shuttle.