Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Influence of electrolyte cations on electron transport and electron transfer in dye-sensitized solar cells

The influence of different electrolyte cations ((Li+, Na+, Mg2+, tetrabutyl ammonium (TBA+)) on the TiO2 conduction band energy (Ec) the effective electron lifetime (τn), and the effective electron diffusion coefficient (Dn) in dye-sensitized solar cells (DSCs) was studied quantitatively. The separation between Ec and the redox Fermi level, EF,redox, was found to decrease as the charge/radius ratio of the cations increased. Ec in the Mg2+ electrolyte was found to be 170 meV lower than that in the Na+ electrolyte and 400 meV lower than that in the TBA+ electrolyte. Comparison of Dn and τn in the different electrolytes was carried out by using the trapped electron concentration as a measure of the energy difference between Ec and the quasi-Fermi level, nEF, under different illumination levels. Plots of Dn as a function of the trapped electron density, nt, were found to be relatively insensitive to the electrolyte cation, indicating that the density and energetic distribution of electron traps in TiO2 are similar in all of the electrolytes studied. By contrast, plots of τn versus nt for the different cations showed that the rate of electron back reaction is more than an order of magnitude faster in the TBA+ electrolyte compared with the Na+ and Li+ electrolytes. The electron diffusion lengths in the different electrolytes followed the sequence of Na+ > Li+ > Mg2+ > TBA+. The trends observed in the AM 1.5 current–voltage characteristics of the DSCs are rationalized on the basis of the conduction band shifts and changes in electron lifetime.

Blocking layer optimisation of poly(3-hexylthiopene)based solid state dye sensitized solar cells

The optimisation study of the fabrication of a compact TiO2 blocking layer (via Spray Pyrolysis Deposition) for poly (3-hexylthiopene) (P3HT) for Solid State Dye Sensitized Solar Cells (SDSCs) is reported. We used a novel spray TiO2 precursor solution composition obtained by adding acetylacetone to a conventional formulation (Diisopropoxytitanium bis (acetylacetonate) in ethanol). By Scanning Electron Microscopy a TiO2 layer with compact morphology and thickness of around 100 nmis shown. Through a Tafel plot analysis an enhancement of the device diode-like behaviour induced by the acetylacetone blocking layer respect to the conventional one is observed. Significantly, the device fabricatedwith the acetylacetone blocking layer shows an overall increment of the cell performance with respect to the cellwith the conventional one (DJsc/Jsc = +13.8%, DFF/FF = +39.7%, DPCE/PCE = +55.6%). A conversion efficiency optimumis found for 15 successive spray cycles where the diode-like behaviour of the acetylacetone blocking layer is more effective. Over three batches of cells (fabricated with P3HT and dye D35) an average conversion efficiency value of 3.9% (under a class A sun simulator with 1 sun A.M. 1.5 illumination conditions) was measured. From the best cell we fabricated a conversion efficiency value of 4.5% was extracted. This represents a significant increment with respect to previously reported values for P3HT/dye D35 based SDSCs.

ZnO nanocones with high-index {101̅1} facets for enhanced energy conversion efficiency of dye-sensitized solar cells

ZnO is a promising photoanode material for dye-sensitized solar cells (DSCs) due to its high bulk electron mobility and because different geometrical structures can easily be tailored. Although various strategies have been taken to improve ZnO-based DSC efficiencies, their performances are still far lower than TiO2 counterparts, mainly because low conductivity Zn2+–dye complexes form on the ZnO surfaces. Here, cone-shaped ZnO nanocrystals with exposed reactive O-terminated {101̅1} facets were synthesized and applied in DSC devices. The devices were compared with DSCs made from more commonly used rod-shaped ZnO nanocrystals where {101̅0} facets are predominantly exposed. When cone-shaped ZnO nanocrystals were used, DSCs sensitized with C218, N719, and D205 dyes universally displayed better power conversion efficiency, with the highest photoconversion efficiency of 4.36% observed with the C218 dye. First-principles calculations indicated that the enhanced DSCs performance with ZnO nanocone photoanodes could be attributed to the strength of binding between the dye molecules and reactive O-terminated {101̅1} ZnO facets and that more effective use of dye molecules occurred due to a significantly less dye aggregation on these ZnO surfaces compared to other ZnO facets.

One-step synthesis of titanium oxide with trilayer structure for dye-sensitized solar cells

Titanium oxide films with trilayer structure grown on fluorine doped tin oxide substrate were prepared from one-step hydrothermal process. The trilayer structure consists of microflowers, nanorod array and compact nanoparticulates, which is expected to possess the merits of good light harvesting, a high electron transport rate, while avoiding the issues of electron shunting. The photovoltaic performance was comprehensively studied and a 60% enhancement in short circuit photocurrent density was found from microflowers contribution as a light scattering layer. This unique trilayer structure exhibits great potential application in future dye-sensitized solar cells.

Enhanced electron lifetime of CdSe/CdS quantum dot (QD) sensitized solar cells using ZnSe core–shell structure with efficient regeneration of quantum Ddots

Research on development of efficient passivation materials for high performance and stable quantum dot sensitized solar cells (QDSCs) is highly important. While ZnS is one of the most widely used passivation material in QDSCs, an alternative material based on ZnSe which was deposited on CdS/CdSe/TiO2 photoanode to form a semi-core/shell structure has been found to be more efficient in terms of reducing electron recombination in QDSCs in this work. It has been found that the solar cell efficiency was improved from 1.86% for ZnSe0 (without coating) to 3.99% using 2 layers of ZnSe coating (ZnSe2) deposited by successive ionic layer adsorption and reaction (SILAR) method. The short circuit current density (Jsc) increased nearly 1-fold (from 7.25 mA/cm2 to13.4 mA/cm2), and the open circuit voltage (Voc) was enhanced by 100 mV using ZnSe2 passivation layer compared to ZnSe0. Studies on the light harvesting efficiency (ηLHE) and the absorbed photon-to-current conversion efficiency (APCE) have revealed that the ZnSe coating layer caused the enhanced ηLHE at wavelength beyond 500 nm and a significant increase of the APCE over the spectrum 400−550 nm. A nearly 100% APCE was obtained with ZnSe2, indicating the excellent charge injection and collection process in the device. The investigation on charge transport and recombination of the device has indicated that the enhanced electron collection efficiency and reduced electron recombination should be responsible for the improved Jsc and Voc of the QDSCs. The effective electron lifetime of the device with ZnSe2 was nearly 6 times higher than ZnSe0 while the electron diffusion coefficient was largely unaffected by the coating. Study on the regeneration of QDs after photoinduced excitation has indicated that the hole transport from QDs to the reduced species (S2−) in electrolyte was very efficient even when the QDs were coated with a thick ZnSe shell (three layers). For comparison, ZnS coated CdS/CdSe sensitized solar cell with optimum shell thickness was also fabricated, which generated a lower energy conversion efficiency (η = 3.43%) than the ZnSe based QDSC counterpart due to a lower Voc and FF. This study suggests that ZnSe may be a more efficient passivation layer than ZnS, which is attributed to the type II energy band alignment of the core (CdS/CdSe quantum dots) and passivation shell (ZnSe) structure, leading to more efficient electron−hole separation and slower electron recombination.

3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Morphology-controllable 1D–3D nanostructured TiO2 bilayer photoanodes for dye-sensitized solar cells

Morphology-controlled bilayer TiO2 nanostructures consisting of one-dimensional (1D) nanowire bottom arrays and a three-dimensional (3D) dendritic microsphere top layer were synthesized via a one-step hydrothermal method. These novel 1D-3D bilayer photoanodes demonstrated the highest energy conversion efficiency of 7.2% for rutile TiO2 dye-sensitized solar cells to date, with TiCl4 post-treatment.

Structurally stabilized mesoporous TiO2 nanofibres for efficient dye-sensitized solar cells

One-dimensional (1D) TiO2 nanostructures are very desirable for providing fascinating properties and features, such as high electron mobility, quantum confinement effects, and high specific surface area. Herein, 1D mesoporous TiO2 nanofibres were prepared using the electrospinning method to verify their potential for use as the photoelectrode of dye-sensitized solar cells (DSSCs). The 1D mesoporous nanofibres, 300 nm in diameter and 10-20 μm in length, were aggregated from anatase nanoparticles 20-30 nm in size. The employment of these novel 1D mesoporous nanofibres significantly improved dye loading and light scattering of the DSSC photoanode, and resulted in conversion cell efficiency of 8.14%, corresponding to an ∼35% enhancement over the Degussa P25 reference photoanode.

Improved photovoltaic performance of dye-sensitized solar cells with modified self-assembling highly ordered mesoporous TiO 2 photoanodes

Strategies for improving the photovoltaic performance of dye-sensitized solar cells (DSSCs) are proposed by modifying highly transparent and highly ordered multilayer mesoporous TiO 2 photoanodes through nitrogen-doping and top-coating with a light-scattering layer. The mesoporous TiO 2 photoanodes were fabricated by an evaporation-induced self-assembly method. In regard to the modification methods, the light-scattering layer as a top-coating was proved to be superior to nitrogen-doping in enhancing not only the power conversion efficiency but also the fill factor of DSSCs. The optimized bifunctional photoanode consisted of a 30-layer mesoporous TiO 2 thin film (4.15 μm) and a Degussa P25 light-scattering top-layer (4 μm), which gives rise to a ∼200% higher cell efficiency than for unmodified cells and a fill factor of 0.72. These advantages are attributed to its higher dye adsorption, better light scattering, and faster photon-electron transport. Such a photoanode configuration provides an efficient way to enhance the energy conversion efficiency of DSSCs.

Continually adjustable oriented 1D TiO2 nanostructure arrays with controlled growth of morphology and their application in dye-sensitized solar cells

Oriented, single-crystalline, one-dimensional (1D) TiO2 nanostructures would be most desirable for providing fascinating properties and features, such as high electron mobility or quantum confinement effects, high specific surface area, and even high mechanical strength, but achieving these structures has been limited by the availability of synthetic techniques. In this study, a concept for precisely controlling the morphology of 1D TiO2 nanostructures by tuning the hydrolysis rate of titanium precursors is proposed. Based on this innovation, oriented 1D rutile TiO2 nanostructure arrays with continually adjustable morphologies, from nanorods (NRODs) to nanoribbons (NRIBs), and then nanowires (NWs), as well as the transient state morphologies, were successfully synthesized. The proposed method is a significant finding in terms of controlling the morphology of the 1D TiO2 nano-architectures, which leads to significant changes in their band structures. It is worth noting that the synthesized rutile NRIBs and NWs have a comparable bandgap and conduction band edge height to those of the anatase phase, which in turn enhances their photochemical activity. In photovoltaic performance tests, the photoanode constructed from the oriented NRIB arrays possesses not only a high surface area for sufficient dye loading and better light scattering in the visible light range than for the other morphologies, but also a wider bandgap and higher conduction band edge, with more than 200% improvement in power conversion efficiency in dye-sensitized solar cells (DSCs) compared with NROD morphology.

Kinetics of electron recombination of dye-senitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO2 films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dye N719, C218 and D205 respectively have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τn, of the N719 based NR-DSSC is the lowest whereas the τn of the C218 based NR-DSSC is the highest among the three dyes. The higher Voc with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO2 film. In addition, in comparison to the DSSCs with conventional nanocrystalline particles based TiO2 films, the NR-DSSCs have shown over two orders of magnitude higher τn when employing N719 as the sensitizer. Nevertheless, the τn of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than the that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.

Solid-state nanocrystalline dye-sensitized solar cell using 2-mercapto benzimidazole doped poly(ethylene oxide) as a new polymer electrolyte

New composite doped poly (ethylene oxide) polymer electrolyte was developed using 2-mercapto benzimidazole as plasticizer and iodide/triiodide as redox couple. The fabrication of the cell involves Poly(ethylene oxide)/ 2-mercapto benzimidazole / iodide/triiodide as polymer electrolyte in dye-sensitized solar cell fabricated with N3 dye and TiO2 nanoparticles as the photoanode and Platinum coated FTO (fluorine doped SnO2) as counter electrode. The current-volatage characteristics under simulated sunlight AM1.5 shows a short circuit current Isc of 8.7mA and open circuit photovoltage 508 mV. The conductivity measurements for the new polymer electrolyte and the photoelectrochemical measurments were carried out systematically. In 2-mercapto benzimidazole the electron rich sulphur and nitrogen atoms, act as pi-electron donors that form good interaction with iodine which plays a vital role in the performance of the fabricated dye-sensitized solar cells. The resonance effect increases the stability of the cell to a considerable extent. These results suggest that the new composite polymer electrolyte performs as a promising new doped polymer-electrolyte.

Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]