Mine Memesa

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.

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.

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.

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.

Integrated blocking layers for hybrid organic solar cells

In hybrid organic solar cells a blocking layer between transparent electrode and nanocrystalline titania particles is essential to prevent short-circuiting and current loss through recombination at the electrode interface. Here we report the preparation of a thin, uniform and crack free hybrid blocking layer composed of conducting titania nanoparticles embedded in an insulating polymer derived ceramic. To do so we combine sol–gel chemistry with novel poly(dimethylsiloxane) containing amphiphilic block copolymer, poly(ethyleneglycol) methyl ether methacrylate–block–poly(dimethylsiloxane)–block–poly(ethyleneglycol) methyl ether methacrylate as the templating agent. Conductive probe scanning force microscopy proved that the existing percolating titania networks are separated by an insulating ceramic matrix. The structural uniformity of the percolating structures was investigated by microbeam grazing incidence small angle X-ray scattering making the integrated blocking layer suitable for hybrid organic solar device applications. Preliminary tests with the integrated blocking layer showed reasonable comparison to conventional TiO2 blocking layer containing devices mentioned in the literature.

Layer-by-layer fabrication of an anatase titania multilayer with gradual sponge-like morphology

The fabrication of a functional multilayer system with a gradually hierarchical order formed by individual titania thin films of different porosity is investigated. The porous or sponge-like nanostructures are fabricated using a diblock copolymer assisted sol–gel process. The successive spin-coating of the sol–gel solution onto the silicon substrate deposits a thin polymer nanocomposite film which is transformed to purely anatase titania nanostructures via calcination. In total, this procedure is repeated layer by layer for three times. This layer-by-layer approach is monitored with grazing incidence small-angle X-ray scattering (GISAXS) after each fabrication step. The GISAXS investigation is complemented in real space with a scanning electron microscopy characterization of the respective preparation stages. From the characterization, a porous titania multilayer system with gradually structured levels is clearly identified.

Integrated Spin‐on Barrier Layers a Reasonable Idea?

Titanium dioxide (TiO2) nanoparticles were prepared using a polystyrene‐block‐polyethyleneoxide copolymer as a template. As a preliminary study whether polydimethylsiloxane (PDMS) is a suitable polymeric replacement for barrier layers, PDMS was spin coated over the TiO2 nanoparticles and subsequently etched by oxygen plasma. The surface characteristics of the particles were investigated using Scanning Electron Microscopy and photoluminescence (PL). The PL measurements indicated the formation of exciton traps close to the particle surface after plasma treatment. The stability of the TiO2 nanoparticles upon sealing with PDMS followed by etching of the polymer overcoating was confirmed with microbeam grazing incidence small angle X‐ray scattering measurements.