UV light protection through TiO2 blocking layers for inverted organic solar cells

Fully organic solar cells (OSCs) based on polymers and fullerenes have attracted remarkable interest during the last decade and high power conversion efficiencies (PCEs) beyond 8% have been realized. However, air stability of these cells remains poor. The conventional geometry of OSCs utilizes strongly oxidizing metal top contacts like Al or Ca. These metals are easily oxidized in air resulting in rapid decrease of PCE if cells are not perfectly encapsulated. Using a thin electron-selective hole-blocking bottom layer like TiO₂ enables fabrication of solar cells in a so-called inverted geometry. In this geometry, noble metals like Ag or Au can be used as top contacts, which are less sensitive to ambient oxygen. Thus, air-stability of these inverted solar cells is significantly improved. In this study we investigate inverted polythiophene-methanofullerene solar cells. We find significant influence of the TiO₂ layer thickness on light absorption and illumination stability of the solar cells, as well as the trap filling by photoinduced carriers. Even though TiO₂ layers as thick as 500 nm seem not to be detrimental for charge transport, light intensity losses limit the device performance. In turn, illumination stability is better for thicker TiO₂ layers, which can serve as UV filters and protect the photoactive materials from degradation, when compared to thin TiO₂ layers. Considering these different effects we state that a thickness of 100 nm is the optimization of the TiO₂ layer.     

Oxide/polymer interfaces for hybrid and organic solar cells: Anatase vs. Rutile TiO2

In this work, we study the effect of the transparent conducting oxide (TCO) and the polymer applied (MEH-PPV or P3HT) on the photovoltaic properties of TCO/TiO₂/polymer/Ag bi-layer solar cells. The solar cells were analyzed under inert atmosphere conditions resembling an encapsulated or sealed device. We demonstrate that the substrate applied, ITO or FTO, modifies the crystalline structure of the TiO₂: on an ITO substrate, TiO₂ is present in its anatase phase, on an FTO, the rutile phase predominates. Devices fabricated on an FTO, where the rutile phase is present, show better stability under inert atmospheres than devices fabricated on an ITO, anatase phase. With respect to the polymer, devices based on MEH-PPV show higher Voc (as high as 1 V), while the application of P3HT results in lower Voc, but higher J_sc and longer device stability. These observations have been associated to (a), the crystalline structure of TiO₂ and (b) to the form the polymer is bonded to the TiO₂ surface. In-situ IPCE analyses of P3HT-based solar cells show a red shift on the peak corresponding to TiO₂, which is not present on the MEH-PPV-based solar cells. The latter suggest that P3HT can be linked to the TiO₂ though the S-end atom, which results in devices with lower Voc. All these observations are also valid for devices, where the bare TiO₂ is replaced by an Nb-TiO₂. The application of an Nb-TiO₂ with rutile structure in these polymer/oxide solar cells is the reason for their higher stability under inert atmospheres. We conclude that the application of TiO₂ in its rutile phase is beneficial for long-term stability devices. Moreover there is an interplay between low Voc and J_sc in devices applying P3HT, since power conversion efficiency can be partially canceled by their lower Voc in comparison with MEH-PPV. These findings are important for polymer/oxide solar cells, but also for organic solar cells, where a layer of semiconductor oxides are in direct contact with a polymer, like in an inverted or tandem organic solar cells.     

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.     

A hybridized electron-selective layer using Sb-doped SnO2 nanowires for efficient inverted polymer solar cells

We developed a novel hybridized electron-selective layer comprised of Sb-doped SnO₂ nanowires for efficient inverted polymer solar cells. A device containing Sb-doped SnO₂ nanowires with 0.1 mg/ml concentration showed a significant increase in power conversion efficiency to 3.23% with an enhanced fill factor, compared to a reference device without the nanowires (2.89%). Such improvement is attributed to the high electrical conductivity of one-dimensional Sb-doped SnO₂ nanowires and to the good light transmittance through the wide band gap of tin oxide. Also the surface morphology of the hybridized electron-selective layer is made denser and improved by incorporating one-dimensional Sb-doped SnO₂ nanowires, resulting in the enhancement of the photovoltaic performance.     

TiO2 films obtained by microwave-activated chemical-bath deposition used to improve TiO2-conducting glass contact

In traditional solar cells, metal-semiconductor contacts used to extract photogenerated carriers are very important. In dye-sensitized solar cells (DSSC) not much attention has been given to contact between the TiO₂ and the transparent conducting glass (TCO), which is used instead of a metal contact to extract electrons. TiO₂ layers obtained by microwave-activated chemical-bath deposition (MW-CBD) are proposed to improve TiO₂ contact to conducting glass. Spectra of incident photon to current conversion efficiency (IPCE) are obtained for two-photoelectrode TiO₂ photoelectrochemical cells. IPCE spectra show higher values when TiO₂ double layer photoelectrodes are used. In these, the first layer or contacting layer is made by MW-CBD. Best results are obtained for double layer photoelectrodes on FTO (SnO₂:F) as conducting oxide substrate. Modeling of IPCE spectra reveals the importance of electrical contact and electron extraction rate at the TiO₂/TCO interface.     

Comparison of various sol-gel derived metal oxide layers for inverted organic solar cells

Inverted bulk-heterojunction solar cells have recently captured high interest due to their environmental stability as well as compatibility to mass production. This has been enabled by the development of solution processable n-type semiconductors, mainly TiO₂ and ZnO. However, the device performance is strongly correlated to the electronic properties of the interfacial materials, and here specifically to their work function, surface states as well as conductivity and mobility. It is noteworthy to say that these properties are massively determined by the crystallinity and stoichiometry of the metal oxides. In this study, we investigated aluminum-doped zinc oxide (AZO) as charge selective extraction layer for inverted BHJ solar cells. Thin AZO films were characterized with respect to their structural, optical and electrical properties. The performance of organic solar cells with an AZO electron extraction layer (EEL) is compared to the performance of intrinsic ZnO or TiO_x EELs. We determined the transmittance, absorbance, conductivity and optical band gap of all these different metal oxides. Furthermore, we also built the correlations between doping level of AZO and device performance, and between annealing temperature of AZO and device performance.     

Hybrid poly (3-hexylthiophene)/titanium dioxide nanorods material for solar cell applications

We conducted an extensive study on poly(3-hexylthiophene) (P3HT) in combination with titanium dioxide (TiO₂) nanorods hybrid material for polymer solar cell applications. The device performance critically depends on the morphology of the hybrid film that will be determined by the molecular weight of P3HT, the solvent type, the hybrid compositions, the surface ligand on the TiO₂ nanorods, film thickness, process conditions, and so on. The current–voltage characteristic of the device fabricated in air has shown a power conversion efficiency of 0.83% under air mass (AM) 1.5 illumination using high molecular weight (65,000 D) P3HT, high boiling point solvent trichlorobenzene, and pyridine-modified TiO₂ nanorods with a film thickness of about 100 nm. The Kelvin probe force microscopy (KPFM) study of hybrid films shows large-scale phase separation with domain size greater than 10 nm, which may be the main factor limiting device performance.     

Organic solar cells incorporating buffer layers from indium doped zinc oxide nanoparticles

Monodisperse, indium doped zinc oxide (IZO) nanoparticles were prepared via the polyol-mediated synthesis and incorporated into regular and inverted poly-(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl C₆₁-butyric acid methyl ester organic photovoltaic devices as buffer layers between the active layer and the cathode. Efficient hole blocking at the particle buffer layers leads to an enhanced open-circuit voltage of the solar cells. This effect is even more pronounced for inverted device architectures. Device degradation studies revealed a solar cell performance reduction upon sample exposition to ambient atmosphere. However, this degradation is fully reversible under UV illumination. In addition, the n-doped IZO particles form suitable charge carrier transport layers for an efficient recombination in an intermediate recombination zone in tandem solar cells. Accordingly we have fabricated fully solution-processed tandem solar cells and investigated their optoelectronic properties.     

Surface treated TiO2 nanorod arrays for the improvement of water splitting

Water splitting is widely employed for the hydrogen production for its abundant sources of water and sunlight. The TiO₂ nanostructures are the most promising materials because of their properties of the non-toxicity and relatively low cost. Surface treatments with TiCl₄ solution and titanium butoxide solution are applied on the TiO₂ nanorod arrays respectively. On the surface of the TiO₂ nanorods, TiO₂ nanoparticles are prepared through hydrolysis of TiCl₄ and homogeneous phase of TiO₂ synthesized with assist of second hydrothermal synthesis in titanium butoxide, resulting in the increase of the surface area of the TiO₂. Comparing with that of the original TiO₂ nanorod arrays, the incident photon-to-electron conversion efficiency (IPCE) of the TiO₂–TiCl₄ and TiO₂–H₂O samples is greatly enhanced by 25% and 250% in the ultraviolet region, respectively. The obviously enhanced activity is due to the larger surface structure after treatments, which could contribute to the improved performance in the water splitting. These surface treatments provide an efficient way to regulate the properties of the TiO₂ nanorod arrays for their extensive applications in the solar device for the hydrogen production.     

Semitransparent inverted polymer solar cells using MoO3/Ag/WO3 as highly transparent anodes

We demonstrate semitransparent inverted polymer solar cells with highly transparent anodes. The structure of the anode is made up of molybdenum trioxide (MoO₃)/silver (Ag)/tungsten oxide (WO₃). The inner MoO₃ layer is introduced as a buffer layer to improve hole collection, while the outer WO₃ layer serves as a light coupling layer to enhance optical transmittance of the photovoltaic device. The dependence of device performances on thickness of the outer WO₃ layer was investigated, and the transmittance and reflectance of MoO₃ (1 nm)/Ag(10 nm)/WO₃(x=0, 20, 40, 60, and 80 nm) electrode are compared. A high transmission of 90% was achieved for semitransparent inverted polymer solar cells with a 40 nm thick outer WO₃ layer.     

Down-conversion Ce-doped TiO2 nanorod arrays and commercial available carbon based perovskite solar cells: Improved performance and UV photostability

Ce-doped TiO₂ nanorod arrays as the mesoporous supporting layer and TiO₂ compacted electron blocking layer was simultaneously fabricated by one-pot hydrothermal method. Ce-doped TiO₂ nanorod was utilized as down-conversion luminescence centers and commercial available carbon was used in hole-transport-free perovskite solar cells. SEM indicated that the doping of Ce reduced the diameter of TiO₂ nanorods. XRD and EDS spectra demonstrate the successful incorporation of Ce ions. UV–Vis absorption spectra and PL emission spectra show that the down-conversion center Ce⁴⁺ can effectively utilize ultraviolet light and extend the absorption into the ultraviolet region. The carbon-based device using the optimized Ce doping concentration achieved power conversion efficiency (PCE) of 10.1%, which was 24.6% higher than that of undoped device. Ce doping changes the band gap of TiO₂ and the Fermi energy level, and thus improve the open circuit voltage. The open circuit voltage decay curve show that Ce-doped TiO₂ prolongs electron lifetime. EIS analysis hints that more carriers are generated. The UV stability has also been significantly improved., PCE of the optimized Ce-doped device still retains 90% of the initial value, however, the undoped device decreases to 55% of the initial value under light irradiation at ambient atmosphere for 12 h.     

Single crystalline TiO2 nanorods with enhanced visible light activity for solar hydrogen generation

Single crystalline TiO₂ nanorods and polycrystalline nanotubes were fabricated with same length to investigate the effects of their nanostructures on photocatalytic properties for splitting water. In order to enhance the visible light absorbance, TiO₂ nanorods and nanotubes were sensitized with semiconductor nanoparticles such as CdS, CdSe, and CdS/CdSe, and compared in viewpoint of solar hydrogen generation. It was observed that single-crystalline nanorods showed superior photocatalytic properties to polycrystalline nanotubes, and also the potential level of the nanorods with rutile phase was measured as lower than that of the nanotubes with mixture of anatase and rutile. Further improvement of photo-conversion efficiency was obtained by subsequent heat treatments of the sensitized photoelectrodes. It turns out that the improvement is attributed to the improved crystallinity and the increased size of the nanoparticles during the post-annealing treatments. It was demonstrated that TiO₂ nanorods with lower potential level and a single crystalline phase on FTO glass were advantageous for effective charge injection from the sensitized nanoparticles and transport without recombination lost at grain boundaries.     

Enhanced heterogeneous ferrioxalate photo-fenton degradation of reactive orange 4 by solar light

A combined homogeneous and heterogeneous photocatalytic decolourisation and degradation of a chlorotriazine Reactive azo dye Reactive Orange 4 (RO4) have been carried out using ferrous sulphate/ ferrioxalate with H₂O₂ and TiO₂-P25 particles. Solar/ferrous/H₂O₂/TiO₂-P25 and solar/ferrioxalate/H₂O₂/TiO₂-P25 processes are found to be more efficient than the individual photo-Fenton and solar/TiO₂-P25 processes. A comparison of these two processes with UV/ferrous/H₂O₂/TiO₂-P25 and UV/ferrioxalate/H₂O₂/TiO₂-P25 reveals that ferrioxalate is more efficient in solar light whereas ferrous ion is more efficient in UV light. The experimental parameters such as pH, initial H₂O₂, Fe²⁺, ferrioxalate and TiO₂-P25 concentration strongly influenced the dye removal rate in solar processes. The optimum operating conditions of these two combined processes are reported.     

Enhancement of photoelectrochemical response by Au modified in TiO2 nanorods

We report on the design and synthesis of a novel Au/TiO₂/Au heterostructure and its implementation as a photoanode for photoelectrochemical (PEC) application. The Au/TiO₂/Au heterostructure was produced by assembling Au nanoparticles and TiO₂ nanorods (NRs) onto FTO substrate, followed by electrodepositing Au nanoparticles on the TiO₂NRs. Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize the prepared photoanodes. Compared to the system involving Au nanoparticles directly linked to TiO₂, this Au/TiO₂/Au heterostructure exhibits significant improved photoresponse as a photoanode, as demonstrated good performance in PECs. This study illustrates the importance of pre-deposited Au underlayers in influencing PEC properties of hybrid assembled nanostructures. As the Au/TiO₂NRs/Au photoanodes are easily fabricated and highly stable, Au/TiO₂NRs/Au can serve as a good substitution for TiO₂ in a variety of solar energy driven applications including PEC water splitting, photocatalysis, and solar cells.     

Manufacturing method for transparent electric windows using dye-sensitized TiO2 solar cells

The transparent electric windows based on dye-sensitized nanocrystalline TiO₂ solar cells have been prepared. The solar cell consists of dye-sensitized TiO₂ electrode with a TiO₂ layer of an about 8 μm thickness and of a 80×80 mm² active area, Pt counter electrode and redox electrolyte. The solar cell shows a transmittance of approximately 60% in the visible range and an open-circuit voltage (V_oc) of 0.64 V and a short-circuit photocurrent (J_sc) of 250 mA. A moderately transparent electric window composed of nine unit solar cells in series generates V_oc of 5.7 V and J_sc of 220 mA at one sun light intensity.     

Opto-electrical and morphological characterization of water soluble conjugated polymers for eco-friendly hybrid solar cells

Solid-state Dye-Sensitized Solar Cells (ss-DSSCs) are promising candidates for future low cost photovoltaic energy generation and are based on polymer/metal oxide donor/acceptor heterojunctions. However, a crucial drawback of hybrid solar cells is the use of environmental unfriendly solvents, such as toluene, chloroform, chlorobenzene, etc. in the phase of preparation. In this work towards eco-friendly processing, we use water as a solvent in the preparation of the photo-active layer for hybrid solar cells. We demonstrate eco-friendly hybrid polymer/titania solar cells consisting of water soluble polythiophene as light-absorber, donor and Hole Transporting Layer (HTL), above a TiO₂ layer that acts as an acceptor and electron conductor. The water soluble conjugated polymer materials are studied in terms of their opto-electrical and morphological properties, leading to a better understanding of the resulting photovoltaic performance. An alternative new processing method in device preparation is introduced; yielding prototype solar cells with an efficiency of 0.7%. This promising solar cell device performance can be considered as a proof-of-principle for future eco-friendly solar cells.     

Performance of dye-sensitized solar cell based on nanocrystals TiO2 film prepared with mixed template method

Highly efficient dye-sensitized solar cells were produced using high-crystalline TiO₂ nanoparticles as a thin-film semiconductor prepared with a mixed template of copolymer F127 (poly(ethylene oxide)₁₀₆-poly(propylene oxide)₇₀-poly(ethylene oxide)₁₀₆) and surfactant CTAB (cetyltrimethylammonium bromide) which allows access to larger surface area, smaller size and higher crystallinity TiO₂ particles. The light-to-electricity conversion of the TiO₂ film composed of nanocrystals with the size of 35 nm, which carry out perfect electrical contiguity between film and conducting glass and between every TiO₂ coating, was over 6% with a film of 5.5 μm thickness. Over 8% conversion efficiency has been obtained with a double-layer film composed by the TiO₂ layer and the scattering layer.     

Fabrication and characterization of dye-sensitized solar cells from rutile nanofibers and nanorods

Rutile titania (TiO₂) nanofibers were prepared by electrospinning a polymeric sol containing a titanium precursor and Poly(vinylpyrrolidone) in acetic acid-ethanol mixture and subsequent sintering of the fibers at 800 °C. The resultant continuous, polycrystalline porous fibers contained TiO₂ grains of 15-20 nm sizes. The continuous fibers were broken down into nanorods by mechanical grinding. Morphology of the nanofibers and nanorods was characterized by scanning and transmission electron microscopies. The crystal structure and polycrystallinity of the fibers were further confirmed by X-ray diffraction analysis. Dye-sensitized solar cells (DSCs) fabricated from the nanofibers and rutile nanorods, respectively, showed superior performance with the later.     

Efficient hybrid carboxylated polythiophene/nanocrystalline TiO2 heterojunction solar cells

Efficient hybrid solar cells fabricated from TiO₂, novel carboxylated polythiophene poly (3-thiophenemalonic acid) P3TMA as sensitizer as well as hole conductor and poly (3-hexylthiophene) (P3HT) as hole transporter was described. UV-Vis absorption and morphology of the active layer were investigated. Device J/V characterizations with different P3HT layer thickness were measured and discussed. Efficiency improvements were observed in thinner P3HT layer thickness and with poly[3,4-(ethylenedioxy)-thiophene]:poly(styrene sulfonate) (PEDOT:PSS) as charge collection layer, and such device showed a short-circuit current density of 1.32 mA/cm², an open-circuit voltage of 0.44 V, a fill factor of 0.43, and a energy conversion efficiency of 0.25% at A.M. 1.5 solar illumination (100 mW/cm²).     

Construction of CdSe@TiO2 core‐shell nanorod arrays by electrochemical deposition for efficient visible light photoelectrochemical performance

The CdSe@TiO₂ core‐shell nanorod arrays for photoelectrochemical (PEC) application were designed and constructed by a facile electrochemical deposition strategy. The CdSe@TiO₂ photoanodes exhibit highly efficient PEC performance under visible light irradiation, among which the CdSe shell layer thickness can be precisely adjusted by different electrodeposition time. In comparison with nude TiO₂ nanorods, the optimized CdSe@TiO₂ photoanode (TC‐500) shows a significant saturated photocurrent density of 2.1 mA/cm² at 0 V (vs Ag/AgCl), which is attributed to the good distribution of CdSe nanoparticles on TiO₂ nanorod arrays, the favorable band alignment, and the intimate interfacial interaction between CdSe nanoparticles and TiO₂ nanorods. The introduction of CdSe shell layer does not only improve light absorption ability but also enhances photogenerated charge carrier's transfer and separation. This current work systematically studies the accurate adjustment of CdSe shell layer thickness on TiO₂ nanorod arrays by electrochemical deposition strategy and provides a paradigm to design and fabricate heterostructure composite for PEC application.