Templated TiO2 mesoporous films used as highly efficient photoelectrode in Dye-Sensitized Solar Cells

Doctoral thesis (2013)

The present thesis is dedicated to the synthesis and characterization of the TiO2 semiconductor layer used as photoelectrode in dye-sensitized solar cells (DSSCs), with the aim to improve their ... [more ▼]

The present thesis is dedicated to the synthesis and characterization of the TiO2 semiconductor layer used as photoelectrode in dye-sensitized solar cells (DSSCs), with the aim to improve their photovoltaic efficiencies. DSSCs have been reported by O’Regan and Grätzel in the early nineties as a very promising alternative to conventional silicon devices. Main benefits of these cells are their low cost and their mild manufacturing process. In most of the specific literature, DSSCs are made of TiO2 films prepared by doctor-blade or screen-printing of anatase nanoparticles paste. However due to the random organization of the nanoparticles, pore accessibility by the dye and electrolyte could be incomplete and some anatase crystallites could be not connected impeding electron transfer. The strategy adopted to improve the films properties and thus PV efficiencies involves a surfactant-assisted process allowing the preparation of highly porous layers with well-ordered and accessibles pores as well as improved crystallites connectivity. The main goal of this work is to increase the film surface area and perfectly control the mesostructure in terms of thickness, pore size, pore organization and pore accessibility in order to maximize the adsorption of active dye and the electrolyte infiltration inside the porous network. Special attention was paid to the tuning of the experimental settings such as the relative humidity conditions, the withdrawal speed and the choices of substrate and surfactant. Moreover, for DSSCs applications, TiO2 film has to be crystallized in form of anatase. Perfect balance between high crystallinity and mesostructure preservation was studied in order to enhance the cells efficiencies. Besides, templated films challenge is to obtain thick layers. Indeed, monolayer films are only a few hundred nanometers thick. To increase the film thickness and thus the quantity of active material, a multilayer process was tuned. Special effort was paid to overcome the surface area limitation induced by the repeated thermal treatments applied during multilayer process. We propose an alternative thermal treatment in order to limit the mesostructure degradation. We also define the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Thick films up to 4 µm were prepared from this multilayer process and show excellent efficiency in combination with N-719 dye (6.1%) when compared to values reported in the literature. Such mesostructured templated films were compared in terms of photovoltaic performances with TiO2 nanoparticles films, generally used in DSSCs. In a second part, as the goal of this thesis is to improve the current nanoparticles-based DSSCs and prove the viability of the templating alternative, a comparison of the long-term stability of both technologies was performed. To our knowledge, long-term stability of templated DSSCs has never been reported at this time. However, in case of templated films, the surface area is highly improved and the negative effects of thermal stress, light soaking and UV exposure could be heightened. Due to their higher active interface, templated films are more sensitive than nanoparticles samples to UV illumination, what can be easily solved by the use of a UV filter. However, they are as stable as nanoparticles samples under visible light soaking (UV filtered) and under thermal stress. In addition, cells were characterized by electrochemical impedance spectroscopy (EIS). Templated cells show lower transfer resistance, as well as longer electron lifetime compared to nanoparticles DSSCs. Using templated films in DSSCs is therefore really promising because higher conversion efficiencies are reached without any increase in cells degradation. Finally, stability limitation encountered by DSSCs are mostly related to the use of liquid electrolytes, which can leak out the cell. Solid-state hole transporting materials are investigated in order to overcome this issue. However, in solid-state DSSCs, TiO2 films thickness is limited to a few microns allowing the adsorption of a limited amount of photoactive dye and thus leading to a poor light harvesting. Moreover, solid-state DSSCs are characterized by incomplete electrolyte filling, impeding the dye regeneration. Both limitations further lead to low photovoltaic efficiencies. Due to the surface area improvement as well as the perfect control of the pore organization and the pore size, the templating strategy was investigated to overcome light harvesting and pore filling limitations. Templated films were prepared from different structuring agents. They show an efficient electrolyte infiltration and a two times higher dye loading compared to nanoparticles layers. Corresponding photovoltaic performances in liquid-state and solid-state DSSCs have also been evaluated. While templating allows improving the liquid-state cells efficiencies, we cannot conclude for solid-state DSSCs due to device assembly issue and/or bad contacts between the electrodes and the sample holder during the I-V measurements. We hope that the achievements of this thesis brought a significant contribution to the field of DSSCs. Indeed, the templating strategy is proved to improve the liquid-sate cells efficiency. However, the assembly of solid-state devices and subsequent I-V tests have to be investigated further. Besides, new pathways are envisaged for interesting future work in both fundamental and applied research fields, such as the synthesis of templated films with hierarchical porosity or scale-up and industrialization of the templated devices. [less ▲]

Hierarchical Porous TiO2 thin films by soft and dual templating: A quantitative approach of specific surface and porosity

Poster (2013, March)

Hierarchical porous structures, with different pore sizes, constitute an important field of research for many applications. However, increasing the pore size results in the decrease of specific surface ... [more ▼]

Hierarchical porous structures, with different pore sizes, constitute an important field of research for many applications. However, increasing the pore size results in the decrease of specific surface. There is a need to quantify and predict the resulting porosity and specific surface. We have prepared hierarchical porous TiO2 thin films either by surfactant templating (soft) or dual surfactant/microspheres templating (soft/hard). They all show narrow, bimodal distribution of pores. Soft templating route leads to very thin films showing high specific surface and bimodal porosity with diameters of 10 nm and 54 nm. Dual templating route combines a Pluronic surfactant-based precursor solution with polystyrene (PS) microspheres (diam. 250 nm) in a one-pot simple process. This gives thicker films with a bimodal distribution of pores (8 nm and 165-200 nm). The dye loading of hierarchical films is compared to pure Pluronic-templated TiO2 films and shows a relative decrease of 29% for Single Templating (ST) and 43% for Dual Templating (DT-250). Finally, a geometrical model is proposed and validated for each system, based on the agreement between calculated specific surfaces and experimental dye loading with N719 dye. [less ▲]

TiO2 templated multilayer films used as high efficiency photoelectrode in liquid or solid DSSCs

Conference (2012, April 10)

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes ... [more ▼]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes with a thickness of 10-15 µm. Templated-assisted dip-coating techniques are used to obtain thin films with ordered porosity. However, monolayer films prepared by dip-coating from a solution suffer from a low quantity of active material with a limited surface area, leading to poor photovoltaic performances. Therefore a multilayer deposition process is needed to increase the film thickness along with surface area. Multilayer dip-coating procedures have already been reported but are usually characterized by a lack of linearity in the evolution of parameters (roughness, surface area, PV performances) as the number of layer increases. In this study, we investigate a dip-coating-based multilayer deposition technique delaying these limitations. First, the influence of the template on the film organization and porosity is studied in terms of long-range order, percentage of porosity, pore size, surface area and pores connectivity. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films. The film exhibiting the highest dye loading was selected and its thickness gradually increased up to 4 µm. Finally, the photovoltaic performances of the thick films (1 to 4 µm) have been evaluated in combination with the N719 dye and a liquid electrolyte and show excellent efficiency (6.1%) when compared to values reported in the literature. Such mesostructured films were compared in terms of photovoltaic performance with TiO2 nanoparticles films, generally used in DSSC. Films were further evaluated by Rutherford Backscattering Spectrometry (RBS) as high performance photoelectrode in solid-state DSSCs, in combination with Z907 dye and Spiro-OMeTAD as solid electrolyte. [less ▲]

Microstructural evolution of a TiO2 mesoporous single layer film under calcination: Effect of stabilization and repeated thermal treatments on the film crystallization and surface area

in Thin Solid Films (2012), 520

This study quantifies the highest perturbation encountered by the first layer of a TiO2 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an ... [more ▼]

This study quantifies the highest perturbation encountered by the first layer of a TiO2 12 layers-mesoporous coating, which is submitted to a multistep calcination process. Besides, we propose an alternative thermal treatment in order to limit the degradation induced by repeated calcinations. This paper reports and compares the modifications in film thickness, surface area, anatase crystallite size and global crystallinity of films obtained from different thermal treatments. It defines the maximum crystal size compatible with the preservation of the mesoarchitecture initially induced by templating. Differences in microporosity and rate of crystallization are also discussed. [less ▲]

TiO2 multilayer thick films (up to 4 μm) with ordered mesoporosity: Influence of template on the film mesostructure and use as high efficiency photoelectrode in DSSCs

in Journal of Materials Chemistry (2011), 21(20), 7356-7363

Mesoporous templated anatase thin films are very promising materials to act as photoelectrode in dye-sensitized solar cell. Templated-assisted dip-coating techniques are used to obtain thin films with ... [more ▼]

Mesoporous templated anatase thin films are very promising materials to act as photoelectrode in dye-sensitized solar cell. Templated-assisted dip-coating techniques are used to obtain thin films with ordered porosity. However, monolayer films are very thin and suffer from a low quantity of active material, leading to poor photovoltaic performances. In this paper, a dip-coating-based multilayer deposition technique is reported. First, we have studied the influence of the template on the film organization and porosity in terms of long-range order, percentage of porosity, pore size and pores connectivity. Different techniques such as transmission electron microscopy (TEM), atmospheric poroellipsometry (AEP) and UV-visible absorption spectroscopy (UV-vis.) have been used to describe the microstructural features of the films with a thickness of 1 µm. The film exhibiting the highest dye loading was selected and its thickness gradually increased up to 4 µm. Finally, the photovoltaic performances of the thick films (1 to 4 µm) have been evaluated in combination with the N-719 dye and show excellent efficiency (6.1%) when compared to values reported in the literature. Such mesostructured films are compared in terms of photovoltaic performance with TiO2 nanoparticles films, generally used in DSSC. [less ▲]

TiO2 thin films (1 µm) with ordered porosity used as high performance photoelectrode in DSSC

Poster (2010, July 06)

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes ... [more ▼]

Mesoporous anatase thin films are very promising materials to act as electrode in dye-sensitized solar cells. Randomly oriented nanocrystalline TiO2 particles are usually used to prepare photoelectrodes with a thickness of 10-15 µm. Templated-assisted dip-coating techniques are used to obtain thin films with ordered porosity. The use of different templates influences the film porosity in terms of long-range order, percentage of porosity, pore size and pores connectivity. The photovoltaic performances of the samples have been evaluated. Such mesostructured films are compared in terms of photovoltaic performance with TiO2 nanoparticles films, generally used in DSSC. [less ▲]

Analysis of thin layers for photovoltaic application: Comparison between RBS and ellipsometry on the determination of roughness and porosity

Poster (2010)

TiO2 mesoporous thin films acting as photoelectrode in dye-sensitized solar cells

Conference (2008, December 03)

This study aims at developing thin films of nanocrystalline, mesostructured titanium dioxide in order to build low cost and efficient photovoltaic devices. The synthesis is based on the Evaporation ... [more ▼]

This study aims at developing thin films of nanocrystalline, mesostructured titanium dioxide in order to build low cost and efficient photovoltaic devices. The synthesis is based on the Evaporation Induced-Self Assembly method using titanium isopropoxide as inorganic source, block copolymers as structuring and porogeneous agents and ethanol as solvent. The films were obtained by dip-coating various substrates in the solution. The influence of different experimental parameters, such as dip-coating and ageing relative humidity, withdrawal speed, surfactant:Ti ratio, substrate, was studied. The post-deposition thermal treatment had to be accurately adjusted in order to maximise the crystallisation of the inorganic network while avoiding the collapse of the porous mesostructure. The final structure obtained is discussed in the light of the XRD results combined with TEM analysis. Moreover the cell performance is limited by the film thickness which is mainly responsible of the small amount of absorbed light. Therefore a multilayer deposition process was studied and the as-obtained mesostructure was characterized by TEM, RBS and environmental ellipsometry. [less ▲]

Mesoporous TiO2 thin films for photovoltaic applications

Poster (2008, August)

Thin films of nanocrystalline, mesostructured titanium dioxide are very promising materials to build low cost and efficient photovoltaic devices. TiO2 present a high chemical stability and electronic ... [more ▼]

Thin films of nanocrystalline, mesostructured titanium dioxide are very promising materials to build low cost and efficient photovoltaic devices. TiO2 present a high chemical stability and electronic properties such as photo-induced electronic transfer properties associated with the anatase phase. For many applications, highly porous nanostructured thin films with accessible pores are preferable to dense ones. Indeed, high accessible porosity leads to high surface area increasing the electron transfer surface. [less ▲]