Role of Surface Coverage and Film Quality of the TiO2 Electron Selective Layer for Optimal Hole-Blocking Properties.

Titanium dioxide (TiO2) is a commonly used electron selective layer in thin-film solar cells. The energy levels of TiO2 align well with those of most light-absorbing materials and facilitate extracting electrons while blocking the extraction of holes. In a device, this separates charge carriers and reduces recombination. In this study, we have evaluated the hole-blocking behavior of TiO2 compact layers using charge extraction by linearly increasing voltage in a metal-insulator-semiconductor structure (MIS-CELIV). This hole-blocking property was characterized as surface recombination velocity (S R) for holes at the interface between a semiconducting polymer and TiO2 layer. TiO2 layers of different thicknesses were prepared by sol-gel dip coating on two transparent conductive oxide substrates with different roughnesses. Surface coverage and film quality on both substrates were characterized using X-ray photoelectron spectroscopy and atomic force microscopy, along with its conductive imaging mode. Thicker TiO2 coatings provided better surface coverage, leading to reduced S R, unless the layers were otherwise defective. We found S R to be a more sensitive indicator of the overall film quality, as varying S R values were still observed among the films that looked similar in their characteristics via other methods.

Cross-Linking of Doped Organic Semiconductor Interlayers for Organic Solar Cells: Potential and Challenges.

Solution-processable interlayers are important building blocks for the commercialization of organic electronic devices such as organic solar cells. Here, the potential of cross-linking to provide an insoluble, stable, and versatile charge transport layer based on soluble organic semiconductors is studied. For this purpose, a photoreactive tris-azide cross-linker is synthesized. The capability of the small molecular cross-linker is illustrated by applying it to a p-doped polymer used as a hole transport layer in organic solar cells. High cross-linking efficiency and excellent charge extraction properties of the cross-linked doped hole transport layer are demonstrated. However, at high doping levels in the interlayer, the solar cell efficiency is found to deteriorate. Based on charge extraction measurements and numerical device simulations, it is shown that this is due to diffusion of dopants into the active layer of the solar cell. Thus, in the development of future cross-linker materials, care must be taken to ensure that they immobilize not only the host but also the dopants.

Investigation of Well-Defined Pinholes in TiO2 Electron Selective Layers Used in Planar Heterojunction Perovskite Solar Cells.

The recently introduced perovskite solar cell (PSC) technology is a promising candidate for providing low-cost energy for future demands. However, one major concern with the technology can be traced back to morphological defects in the electron selective layer (ESL), which deteriorates the solar cell performance. Pinholes in the ESL may lead to an increased surface recombination rate for holes, if the perovskite absorber layer is in contact with the fluorine-doped tin oxide (FTO) substrate via the pinholes. In this work, we used sol-gel-derived mesoporous TiO2 thin films prepared by block co-polymer templating in combination with dip coating as a model system for investigating the effect of ESL pinholes on the photovoltaic performance of planar heterojunction PSCs. We studied TiO2 films with different porosities and film thicknesses, and observed that the induced pinholes only had a minor impact on the device performance. This suggests that having narrow pinholes with a diameter of about 10 nm in the ESL is in fact not detrimental for the device performance and can even, to some extent improve their performance. A probable reason for this is that the narrow pores in the ordered structure do not allow the perovskite crystals to form interconnected pathways to the underlying FTO substrate. However, for ultrathin (~20 nm) porous layers, an incomplete ESL surface coverage of the FTO layer will further deteriorate the device performance.

Doping-induced carrier profiles in organic semiconductors determined from capacitive extraction-current transients.

A method to determine the doping induced charge carrier profiles in lightly and moderately doped organic semiconductor thin films is presented. The theory of the method of Charge Extraction by a Linearly Increasing Voltage technique in the doping-induced capacitive regime (doping-CELIV) is extended to the case with non-uniform doping profiles and the analytical description is verified with drift-diffusion simulations. The method is demonstrated experimentally on evaporated organic small-molecule thin films with a controlled doping profile, and solution-processed thin films where the non-uniform doping profile is unintentional, probably induced during the deposition process, and a priori unknown. Furthermore, the method offers a possibility of directly probing charge-density distributions at interfaces between highly doped and lightly doped or undoped layers.