High-resolution TEM characterization of ZnO core-shell nanowires for dye-sensitized solar cells

Recently ZnO nanowire films have been used in very promising and inexpensive dye-sensitized solar cells (DSSC). It was found that the performance of the devices can be enhanced by functionalising the nanowires with a thin metal oxide coating. This nm-scale shell is believed to tailor the electronic structure of the nanowire, and help the absorption of the dye. Core-shell ZnO nanowire structures are synthesised at low temperature (below 120°C) by consecutive hydrothermal growth steps. Different materials are investigated for the coating, including Mg, Al, Cs and Zr oxides. High resolution TEM is used to characterise the quality of both the nanowire core and the shell, and to monitor the thickness and the degree of crystallisation of the oxide coating. The interface between the nanowire core and the outer shell is investigated in order to understand the adhesion of the coating, and give valuable feedback for the synthesis process. Nanowire films are packaged into dye-sensitised solar cell prototypes; samples coated with ZrO2 and MgO show the largest enhancement in the photocurrent and open-circuit voltage and look very promising for further improvement. © 2010 IOP Publishing Ltd.

A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate.

This paper describes a new strategy to make a full solid-state, flexible, dye-sensitized solar cell (DSSC) based on novel ionic liquid gel, organic dye, ZnO nanoparticles and carbon nanotube (CNT) thin film stamped onto a polyethylene terephthalate (PET) substrate. The CNTs serve both as the charge collector and as scaffolds for the growth of ZnO nanoparticles, where the black dye molecules are anchored. It opens up the possibility of developing a continuous roll to roll processing for THE mass production of DSSCs.

Dye-sensitized solar cells based on a single layer deposition of TiO 2 from a new formulation paste and their photovoltaic performance

A new strategy for enhancing the efficiency and reducing the production cost of TiO 2 solar cells by design of a new formulated TiO 2 paste with tailored crystal structure and morphology is reported. The conventional three- or four-fold layer deposition process was eliminated and replaced by a single layer deposition of TiO 2 compound. Different TiO 2 pastes with various crystal structures, morphologies and crystallite sizes were prepared by an aqueous particulate sol-gel process. Based on simultaneous differential thermal (SDT) analysis the minimum annealing temperature to obtain organic-free TiO 2 paste was determined at 400°C, being one of the lowest crystallization temperatures of TiO 2 photoanode electrodes for solar cell application. Photovoltaic measurements showed that TiO 2 solar cell with pure anatase crystal structure had higher power conversion efficiency (PCE) than that made of pure rutile-TiO 2. However, the PCE of solar cells depends on the anatase to rutile weight ratio, reaching a maximum at a specific value due to the synergic effect between anatase and rutile TiO 2 nanoparticles. Moreover, it was found that the PCE of solar cells made of crystalline TiO 2 powders was much higher, increasing in the range 32-84% depending on anatase to rutile weight ratio, than that of prepared by amorphous powders. TiO 2 solar cell with the morphology of mixtures of nanoparticles and microparticles had higher PCE than the solar cell with the same phase composition containing TiO 2 nanoparticles due to the role of TiO 2 microparticles as light scattering particles. The presented strategy would open up new insight into fabrication and structural design of low-cost TiO 2 solar cells with high power conversion efficiency. © 2012 Elsevier Ltd.

One-pot synthesis of intercalating ZnO nanoparticles for enhanced dye-sensitized solar cells

In this letter we report a facile one-pot synthesis of intercalated ZnO particles for inexpensive, low-temperature solution processed dye-sensitised solar cells. High interconnectivity facilitates enhanced charge transfer between the ZnO nanoparticles and a consequent enhancement in cell efficiency. ZnO thin films were formed from a wide range of nanoparticle diameters which simultaneously increased optical scattering whilst enhancing dye loading. A possible growth mechanism was proposed for the synthesis of ZnO nanoparticles. The intercalated ZnO nanoparticle thin films were integrated into the photoanodes of dye-sensitised solar cells which showed an increase in performance of 37% compared to structurally equivalent cells employing ZnO nanowires. © 2012 Elsevier B.V.

The influence of 1D, meso- and crystal structures on charge transport and recombination in solid-state dye-sensitized solar cells

We have prepared single crystalline SnO2 and ZnO nanowires and polycrystalline TiO2 nanotubes (1D networks) as well as nanoparticle-based films (3D networks) from the same materials to be used as photoanodes for solid-state dye-sensitized solar cells. In general, superior photovoltaic performance can be achieved from devices based on 3-dimensional networks, mostly due to their higher short circuit currents. To further characterize the fabricated devices, the electronic properties of the different networks were measured via the transient photocurrent and photovoltage decay techniques. Nanowire-based devices exhibit extremely high, light independent electron transport rates while recombination dynamics remain unchanged. This indicates, contrary to expectations, a decoupling of transport and recombination dynamics. For typical nanoparticle-based photoanodes, the devices are usually considered electron-limited due to the poor electron transport through nanocrystalline titania networks. In the case of the nanowire-based devices, the system becomes limited by the organic hole transporter used. In the case of polycrystalline TiO2 nanotube-based devices, we observe lower transport rates and higher recombination dynamics than their nanoparticle-based counterparts, suggesting that in order to improve the electron transport properties of solid-state dye-sensitized solar cells, single crystalline structures should be used. These findings should aid future design of photoanodes based on nanowires or porous semiconductors with extended crystallinity to be used in dye-sensitized solar cells. © 2013 The Royal Society of Chemistry.

Optimizing the energy offset between dye and hole-transporting material in solid-state dye-sensitized solar cells

The power-conversion efficiency of solid-state dye-sensitized solar cells can be optimized by reducing the energy offset between the highest occupied molecular orbital (HOMO) levels of dye and hole-transporting material (HTM) to minimize the loss-in-potential. Here, we report a study of three novel HTMs with HOMO levels slightly above and below the one of the commonly used HTM 2,2′,7,7′- tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- spirobifluorene (spiro-OMeTAD) to systematically explore this possibility. Using transient absorption spectroscopy and employing the ruthenium based dye Z907 as sensitizer, it is shown that, despite one new HTM showing a 100% hole-transfer yield, all devices based on the new HTMs performed worse than those incorporating spiro-OMeTAD. We further demonstrate that the design of the HTM has an additional impact on the electronic density of states present at the TiO2 electrode surface and hence influences not only hole- but also electron-transfer from the sensitizer. These results provide insight into the complex influence of the HTM on charge transfer and provide guidance for the molecular design of new materials. © 2013 American Chemical Society.

Dependence of dye regeneration and charge collection on the pore-filling fraction in solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells rely on effective infiltration of a solid-state hole-transporting material into the pores of a nanoporous TiO 2 network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole-transfer yield from the dye to the hole-transporting material 2,2′,7,7′-tetrakis(N,N-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) is shown to rise rapidly with higher pore-filling fractions as the dye-coated pore surface is increasingly covered with hole-transporting material. Once a pore-filling fraction of ≈30% is reached, further increases do not significantly change the hole-transfer yield. Using simple models of infiltration of spiro-OMeTAD into the TiO2 porous network, it is shown that this pore-filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole-transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole-transporting material. Comparison of these results with device parameters shows that improvements of the power-conversion efficiency beyond ≈30% pore filling are not caused by a higher hole-transfer yield, but by a higher charge-collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power-conversion efficiencies with increasing pore-filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro-OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO2 with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore-filling fraction. Solid-state dye-sensitized solar cells capable of complete hole transfer with pore-filling fractions as low as ∼30% are demonstrated. Improvements of device efficiencies beyond ∼30% are explained by a stepwise increase in charge-collection efficiency in agreement with percolation theory. Furthermore, it is predicted that, for a 20 nm pore size, the photocurrent reaches a maximum at ∼83% pore-filling fraction. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increasing the open-circuit voltage of photoprotein-based photoelectrochemical cells by manipulation of the vacuum potential of the electrolytes.

The innately highly efficient light-powered separation of charge that underpins natural photosynthesis can be exploited for applications in photoelectrochemistry by coupling nanoscale protein photoreaction centers to man-made electrodes. Planar photoelectrochemical cells employing purple bacterial reaction centers have been constructed that produce a direct current under continuous illumination and an alternating current in response to discontinuous illumination. The present work explored the basis of the open-circuit voltage (V(OC)) produced by such cells with reaction center/antenna (RC-LH1) proteins as the photovoltaic component. It was established that an up to ~30-fold increase in V(OC) could be achieved by simple manipulation of the electrolyte connecting the protein to the counter electrode, with an approximately linear relationship being observed between the vacuum potential of the electrolyte and the resulting V(OC). We conclude that the V(OC) of such a cell is dependent on the potential difference between the electrolyte and the photo-oxidized bacteriochlorophylls in the reaction center. The steady-state short-circuit current (J(SC)) obtained under continuous illumination also varied with different electrolytes by a factor of ~6-fold. The findings demonstrate a simple way to boost the voltage output of such protein-based cells into the hundreds of millivolts range typical of dye-sensitized and polymer-blend solar cells, while maintaining or improving the J(SC). Possible strategies for further increasing the V(OC) of such protein-based photoelectrochemical cells through protein engineering are discussed.

A quantum dot sensitized solar cell based on vertically aligned carbon nanotube templated ZnO arrays

We report on a quantum dot sensitized solar cell (QDSSC) based on ZnO nanorod coated vertically aligned carbon nanotubes (VACNTs). Electrochemical impedance spectroscopy shows that the electron lifetime for the device based on VACNT/ZnO/CdSe is longer than that for a device based on ZnO/CdSe, indicating that the charge recombination at the interface is reduced by the presence of the VACNTs. Due to the increased surface area and longer electron lifetime, a power conversion efficiency of 1.46% is achieved for the VACNT/ZnO/CdSe devices under an illumination of one Sun (AM 1.5G, 100 mW/cm2). © 2010 Elsevier B.V.