Fabrication and characterization of nanostructured titania films with integrated function from inorganic-organic hybrid materials.

Nanostructured titania films are of growing interest due to their application in future photovoltaic technologies. Therefore, a lot of effort has been put into the controlled fabrication and tailoring of titania nanostructures. The controlled sol-gel synthesis of titania, in particular in combination with block copolymer templates, is very promising because of its high control on the nanostructure, easy application and cheap processing possibilities. This tutorial review gives a short overview of the structural control of titania films gained by using templated sol-gel chemistry and shows how this approach is extended by the addition of further functionality to the films. Different expansions of the sol-gel templating are possible by the fabrication of gradient samples, by the addition of a homopolymer, by the combination with micro-fluidics and also by the application of novel precursors for low-temperature processing. Moreover, hierarchically structured titania films can be fabricated via the subsequent application of several sol-gel steps or via the inclusion of colloidal templates in a one-step process. Integrated function in the block copolymer used in the sol-gel synthesis allows for the fabrication of an integrated blocking layer or an integrated hole-conductor. Both approaches grant a one-step fabrication of two components of a working solar cell, which make them very promising towards a cheap solar cell production route. Looking to the complete solar cell, the top contact is also of great importance as it influences the function of the whole solar cell. Thus, the mechanisms acting in the top contact formation are also reviewed. For all these aspects, characterization techniques that allow for a structural investigation of nanostructures inside the active layers are important. Therefore, the characterization techniques that are used in real space as well as in reciprocal space are explained shortly as well.

Reversible pH-controlled switching of poly(methacrylic acid) grafts for functional biointerfaces.

Responsive polymeric brushes of poly(methacrylic acid) (PMAA) were grafted from silicon surfaces using controlled surface-initiated atom-transfer radical polymerization (SI-ATRP). The growth kinetics of PMAA was investigated with respect to the composition of the ATRP medium by grafting the polymer in mixtures of water and methanol with different ratios. The dissociation behavior of the polymer layers was characterized by FTIR titration after incubating the polymer-grafted substrates in PBS buffer solutions with different pH values. PMAA layers show a strong pH-dependent behavior with an effective pK(a) of the bulk polymer brush of 6.5 ± 0.2, which is independent of the polymer brush thickness and methanol content of the ATRP grafting medium. The pH-induced swelling and collapse of the grafted polymer layers were quantified in real time by in situ ellipsometry in liquid environment. Switching between polymer conformations at pH values of 4 and 8 is rapid and reversible, and it is characterized by swelling factors (maximum thickness/minimum thickness) that increase with decreasing the methanol content of the SI-ATRP medium.

Electrical scanning probe microscopy of an integrated blocking layer.

Scanning probe microscopy was performed on an integrated blocking layer system developed for hybrid organic solar cells. A nanocomposite consisting of titania and an amphiphilic triblock copolymer ((PEO)MA-PDMS-MA(PEO)) was prepared by sol-gel chemistry. After plasma treatment and annealing of a spin casted film of 30-100 nm thickness a granular structure with a typical titania grain diameter of 20 nm was found. Conductive scanning force microscopy revealed that on top of almost every grain on the surface there is an increased conductivity compared to the average value. The correlation of grains and conductivity indicated that titania particles formed interconnecting paths through the film. For the resistivity of these pathways we found that effects of tip-sample and sample-electrode resistivity dominate. Additionally, conductive scanning force microscopy revealed non-conducting structures attributed to the thermal treatment. Kelvin probe microscopy of pristine samples on one side and plasma treated plus annealed samples on the other side showed that there is a shift in work function (0.8 +/- 0.2 eV) as expected for the transition of amorphous to anatase titania.

Preservation of the morphology of a self-encapsulated thin titania film in a functional multilayer stack: an X-ray scattering study.

Tailoring of the titania morphology is achieved by the combination of a triblock copolymer, acting as structure-directing agent, and a sol-gel chemistry enabling the incorporation of the provided inorganic material (titania) into the selected phase of the triblock copolymer. Spin-coating of the solution on FTO-coated glass, followed by plasma etching and calcination of the thin film results in the formation of self-encapsulated crystalline titania nanostructures. The fabricated nanostructures are coated stepwise with dye, conductive polymers and gold forming a functional multilayer stack. An advanced small-angle scattering technique probing the sample with X-ray synchrotron radiation under grazing incidence (GISAXS) is employed for the characterization of the preparation route, as scattering allows accessing the structure inside the multilayers. The tailored titania morphology is preserved during the preparation route towards the functional multilayer stack of a photovoltaic demonstration cell. Two clearly distinguishable structures originate from the substrate and the titania templated by the triblock copolymer; hence the other layers induce no additional structures. Therefore, this investigation provides the evidence that the effort spent to tailor the morphology is justified by the preservation of the self-encapsulated titania morphology that is created by the structure-directing agent throughout the functional multilayer stack build-up.

Morphology and photoluminescence study of titania nanoparticles.

Titania nanoparticles are prepared by sol-gel chemistry with a poly(ethylene oxide) methyl ether methacrylate-block-poly(dimethylsiloxane)-block-poly(ethylene oxide) methyl ether methacrylate triblock copolymer acting as the templating agent. The sol-gel components-hydrochloric acid, titanium tetraisopropoxide, and triblock copolymer-are varied to investigate their effect on the resulting titania morphology. An increased titania precursor or polymer content yields smaller primary titania structures. Microbeam grazing incidence small-angle X-ray scattering measurements, which are analyzed with a unified fit model, reveal information about the titania structure sizes. These small structures could not be observed via the used microscopy techniques. The interplay among the sol-gel components via our triblock copolymer results in different sized titania nanoparticles with higher packing densities. Smaller sized titania particles, (∼13-20 nm in diameter) in the range of exciton diffusion length, are formed by 2% by weight polymer and show good crystallinity with less surface defects and high oxygen vacancies.

Sponge-like structures for application in photovoltaics.

Large surface areas at an interface between two different materials are desired in many research fields where the interaction between these materials significantly affects the performance of the physical system. This behaviour is illustrated on sponge-like structures, which assign for such a high surface area, and demonstrate the development from bulk material to thin films and a variety of applications. The focus is on sponge-like nanostructures consisting of a network of aggregated titania nanoparticles applied in hybrid structures for photovoltaics. Examples based on a sol-gel process for the preparation of titania nanostructures in thin films, mimicking the sponge morphology, are shown. In general, titania films are widely used in photovoltaics, contributing to a large surface area available for interfacial reactions, e.g. charge carrier transfer routes. Interpenetrating networks with dimensions matching exciton diffusion lengths in the polymer component of a hybrid organic-inorganic photovoltaic structure are highly desirable. To characterize the fabricated morphology, atomic force microscopy and field-emission scanning electron microscopy are employed in real space. The advanced scattering technique of grazing-incidence small-angle X-ray scattering complements the characterization in reciprocal space. From the obtained results, the sponge-like morphology is verified, a physical description of the morphology with statistical relevance is constructed and the successful complete filling of the network is shown. According to this description, the presented sponge-like titania nanostructures are well suited for use in hybrid organic-inorganic solar cells.

Hierarchically structured titania films prepared by polymer/colloidal templating.

Hierarchically structured titania films for application in hybrid solar cells are prepared by combining microsphere templating and sol-gel chemistry with an amphiphilic diblock copolymer as a structure-directing agent. The films have a functional structure on three size scales: (1) on the micrometer scale a holelike structure for reduction of light reflection, (2) on an intermediate scale macropores for surface roughening and improved infiltration of a hole transport material, and (3) on a nanometer scale a mesoporous structure for charge generation. Poly(dimethyl siloxane)-block-methyl methacrylate poly(ethylene oxide) (PDMS-b-MA(PEO)) is used as a structure-directing agent for the preparation of the mesopore structure, and poly(methyl methacrylate) (PMMA) microspheres act as a template for the micrometer-scale structure. The structure on all levels is modified by the method of polymer extraction as well as by the addition of PMMA particles to the sol-gel solution. Calcination results in structures with increased size and a higher degree of order than extraction with acetic acid. With addition of PMMA a microstructure is created and the size of the mesopores is reduced. Already moderate microstructuring results in a strong decrease in film reflectivity; a minimum reflectivity value of less than 0.1 is obtained by acetic acid treatment and subsequent calcination.