Tuning the crystallinity parameters in macroporous titania films

Although macroporous titania scaffolds are used for many different applications, not much is known about the importance of the synthesis strategy on the resulting materials' properties. We present a comparative study on the influence of different colloidal titania precursors for direct co-deposition with poly(methyl methacrylate) (PMMA) beads on the properties of the resulting macroporous scaffolds after calcination. The colloidal titania precursors for the film assembly differ in their size and initial crystallinity, ranging from amorphous sol-gel clusters to already crystalline pre-formed particles of 4 nm, 6 nm and 20 nm in size, as well as a combination of sol-gel and nanoparticle precursors in the so-called `Brick and Mortar' approach. The type of the precursor greatly influences the morphology, texture and the specific crystallinity parameters of the macroporous titania scaffolds after calcination such as the size of the crystalline domains, packing density of the crystallites in the macroporous walls and interconnectivity between the crystals. Moreover, the texture and the crystallinity of the films can be tuned by postsynthesis processing of the films such as calcination at different temperatures, which can be also preceded by a hydrothermal treatment. The ability to adjust the porosity, the total surface area and the crystallinity parameters of the crystalline macroporous films by selecting suitable precursors and by applying different post-synthetic treatments provides useful tools to optimize the film properties for different applications

Tuning the crystallinity parameters in macroporous titania films

Although macroporous titania scaffolds are used for many different applications, not much is known about the importance of the synthesis strategy on the resulting materials' properties. We present a comparative study on the influence of different colloidal titania precursors for direct co-deposition with poly(methyl methacrylate) (PMMA) beads on the properties of the resulting macroporous scaffolds after calcination. The colloidal titania precursors for the film assembly differ in their size and initial crystallinity, ranging from amorphous sol-gel clusters to already crystalline pre-formed particles of 4 nm, 6 nm and 20 nm in size, as well as a combination of sol-gel and nanoparticle precursors in the so-called `Brick and Mortar' approach. The type of the precursor greatly influences the morphology, texture and the specific crystallinity parameters of the macroporous titania scaffolds after calcination such as the size of the crystalline domains, packing density of the crystallites in the macroporous walls and interconnectivity between the crystals. Moreover, the texture and the crystallinity of the films can be tuned by postsynthesis processing of the films such as calcination at different temperatures, which can be also preceded by a hydrothermal treatment. The ability to adjust the porosity, the total surface area and the crystallinity parameters of the crystalline macroporous films by selecting suitable precursors and by applying different post-synthetic treatments provides useful tools to optimize the film properties for different applications

Guided in Situ Polymerization of MEH-PPV in Mesoporous Titania Photoanodes

Incorporation of conjugated polymers into porous metal oxide networks is a challenging task, which is being pursued via many different approaches. We have developed the guided in situ polymerization of poly­(2-methoxy-5-(2′-ethylhexyloxy)-<i>p</i>-phenylenevinylene) (MEH-PPV) in porous titania films by means of surface functionalization. The controlled polymerization via the Gilch route was induced by an alkoxide base and by increasing the temperature. The selected and specially designed surface-functionalizing linker molecules mimic the monomer or its activated form, respectively. In this way, we drastically enhanced the amount of MEH-PPV incorporated into the porous titania phase compared to nonfunctionalized samples by a factor of 6. Additionally, photovoltaic measurements were performed. The devices show shunting or series resistance limitations, depending on the surface functionalization prior to in situ polymerization of MEH-PPV. We suggest that the reason for this behavior can be found in the orientation of the grown polymer chains with respect to the titania surface. Therefore, the geometry of the anchoring via the linker molecules is relevant for exploiting the full electronic potential of the conjugated polymer in the resulting hybrid composite. This observation will help to design future synthesis methods for new hybrid materials from conjugated polymers and n-type semiconductors to take full advantage of favorable electronic interactions between the two phases

Spray deposition of titania Films with Incorporated Crystalline Nanoparticles for All-solid-state Dye-Sensitized Solar Cells Using P3HT

Spray coating, a simple and low‐cost technique for large‐scale film deposition, is employed to fabricate mesoporous titania films, which are electron‐transporting layers in all‐solid‐state dye‐sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small‐angle X‐ray scattering, and nitrogen adsorption–desorption isotherms. The crystal phase and crystallite sizes are verified by X‐ray diffraction measurements. The photovoltaic performance of all‐solid‐state DSSCs is investigated. The findings reveal that an optimal active layer of the all‐solid‐state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam‐like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m2 g−1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%.Financial support by TUM.solar in the context of the Bavarian Collaborative Research Project “Solar Technologies Go Hybrid” (SolTech), by the GreenTech Initiative (Interface Science for Photovoltaics – ISPV) of the EuroTech Universities and by the Nanosystems Initiative Munich (NIM) is gratefully acknowledged. V.K. thanks the Bavarian State Ministry of Sciences, Research and Arts for funding this research work via project “Energy Valley Bavaria.” L.S., W.W., and Y.Y. acknowledge the China Scholarship Council (CSC)

Spray Deposition of Titania Films with Incorporated Crystalline Nanoparticles for All-Solid-State Dye-Sensitized Solar Cells Using P3HT

Spray coating, a simple and low-cost technique for large-scale film deposition, is employed to fabricate mesoporous titania films, which are electron-transporting layers in all-solid-state dye-sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small-angle X-ray scattering, and nitrogen adsorption–desorption isotherms. The crystal phase and crystallite sizes are verified by X-ray diffraction measurements. The photovoltaic performance of all-solid-state DSSCs is investigated. The findings reveal that an optimal active layer of the all-solid-state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam-like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m$^2$ g$^{−1}$. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%