Novel Energy Materials and Advanced Characterisation

Abstract:

Perovskite-based photovoltaics are an emerging solar technology with lab scale device efficiencies of over 22 %, and significant steps are being made toward their commercialization. Conventionally high efficiency perovskite solar cells are formed from high boiling point, polar aprotic solvent solutions. Methylammonium lead iodide (CH3NH3PbI3) films can be made from a range of solvents and blends; however, the role the solvent system plays in determining the properties of the resulting perovskite films is poorly understood. Acetonitrile (ACN), in the presence of methylamine (MA), is a viable nontoxic solvent for fabrication of CH3NH3PbI3 photovoltaic devices with efficiencies >18 %. Herein we examine films prepared from ACN/MA and dimethylformamide (DMF) and scrutinize their physical and electronic properties using spectroscopy, scanning probe imaging, and ion scattering. Significant differences are observed in the chemistry and electronic structure of CH3NH3PbI3 films made with each solvent, ACN/MA produces films with superior properties resulting in more efficient photovoltaic devices. Here we present a holistic and complete understanding of a high performance perovskite material from an electronic, physical, and structural perspective and establish a robust toolkit with which to understand and optimize photovoltaic perovskites.

Abstract:

The physical origin of the piezoelectric effect has been the focus of much research work. While it is commonly accepted that the origins of piezoelectricity may be intrinsic (related to the change of lattice parameters) and extrinsic (related to the movement of domain walls), their separation is often a challenging experimental task. Here in situ high-resolution synchrotron X-ray diffraction has been combined with a new data analysis technique to characterize the change of the lattice parameters and domain microstructure of a PbZr1−xTixO3 (x = 0.45) crystal under an external electric field. It is shown how `effective piezoelectric coefficients' evolve upon the transition from purely `intrinsic' effects to `extrinsic' ones due to domain-wall motion. This technique and corresponding data analysis can be applied to broader classes of materials and provide important insights into the microscopic origin of their physical properties.

Abstract:

To date, the most efficient hybrid metal halide peroskite solar cells employ TiO2 as electron-transporting material (ETM), making these devices unstable under UV light exposure. Replacing TiO2 with fullerene derivatives has been shown to result in improved electronic contact and increased device lifetime, making it of interest to assess whether similar improvements can be achieved by using other organic semiconductors as ETMs. In this work, we investigate perylene-3,4:9,10-tetracarboxylic bis(benzimidazole) as a vacuum-processable ETM, and we minimize electron-collection losses at the electron-selective contact by depositing pentamethylcyclopentadienyl cyclopentadienyl rhodium dimer, (RhCp*Cp)2, on fluorinated tin oxide. With (RhCp*Cp)2 as an interlayer, ohmic contacts can be formed, there is interfacial doping of the ETM, and stabilized power conversion efficiencies of up to 14.2% are obtained.

Abstract:

Amorphous TiO2 and SnO2 electron transport layers (ETLs) were deposited by low-temperature atomic layer deposition (ALD). Surface morphology and x-ray photoelectron spectroscopy (XPS) indicate uniform and pinhole free coverage of these ALD hole blocking layers. Both mesoporous and planar perovskite solar cells were fabricated based on these thin films with aperture areas of 1.04 cm2 for TiO2 and 0.09 cm2 and 0.70 cm2 for SnO2. The resulting cell performance of 18.3 % power conversion efficiency (PCE) using planar SnO2 on 0.09 cm2 and 15.3 % PCE using mesoporous TiO2 on 1.04 cm2 active areas are discussed in conjunction with the significance of growth parameters and ETL composition.

Abstract:

PbZr1-xTixO3, which has abundant structural variations in the corresponding physical properties, has been used in a large variety of applications. To understand the effect of the structure on its high-performance piezoelectric properties, its local and average structures are studied. Total scattering data have been obtained from high-energy synchrotron powder diffraction experiments at 20 K and 300 K. Using the reverse Monte Carlo method, information on cation displacements has been extracted from X-ray Pair Distribution Function data. This suggests that the local disorder of the B cations is mainly driven by thermal motion, while the local disorder of Pb is most likely caused by more complex factors, such as displacive disorder. Both rhombohedral and monoclinic local polarizations are observed in Zr-rich PZT, whose directions depend on temperature.