Preparation and manipulation of free-standing oxides for photovoltaic applications.

Epitaxial complex oxides are of great interest for their rich chemical and physical properties, and their functionalities in a wide variety of technology areas. Among them, epitaxial ferroelectric BiFeO_3 has demonstrated huge potential as a new visible light absorber material, pointing the way towards the manufacture of highly efficient photovoltaic devices. However, preparation of complex epitaxial oxides has been essentially limited to specific substrates, hindering the integration of such materials into practical devices on which epitaxial growth cannot be achieved. Here we develop a new solution-based process to prepare Sr_3Al_2O_6 sacrificial layers that can be selectively removed by H_2O. Its feasibility is tested to exfoliate solution processed BiFeO_3 and atomic layer deposited Al_2O_3. By means of X-ray diffraction, atomic force microscopy and scanning transmission electron microscopy, the films have been thoroughly characterized. Also, we performed a study on surface free energy and work of adhesion to transfer the active film to new surfaces, offering a novel platform to optimize the use of this sacrificial layer to freely manipulate complex oxides

Does Sb2Se3 admit nonstoichiometric conditions? How modifying the overall se content affects the structural, optical, and optoelectronic properties of Sb2Se3 thin films

Sb2Se3 is a quasi-one-dimensional (1D) semiconductor, which has shown great promise in photovoltaics. However, its performance is currently limited by a high Voc deficit. Therefore, it is necessary to explore new strategies to minimize the formation of intrinsic defects and thus unlock the absorber’s whole potential. It has been reported that tuning the Se/Sb relative content could enable a selective control of the defects. Furthermore, recent experimental evidence has shown that moderate Se excess enhances the photovoltaic performance; however, it is not yet clear whether this excess has been incorporated into the structure. In this work, a series of Sb2Se3 thin films have been prepared imposing different nominal compositions (from Sb-rich to Se-rich) and then have been thoroughly characterized using compositional, structural, and optical analysis techniques. Hence, it is shown that Sb2Se3 does not allow an extended range of nonstoichiometric conditions. Instead, any Sb or Se excesses are compensated in the form of secondary phases. Also, a correlation has been found between operating under Se-rich conditions and an improvement in the crystalline orientation, which is likely related to the formation of a MoSe2 phase in the back interface. Finally, this study shows new utilities of Raman, X-ray diffraction, and photothermal deflection spectroscopy combination techniques to examine the structural properties of Sb2Se3, especially how well-oriented the material is.Postprint (published version

Challenges and improvement pathways to develop quasi-1D (Sb1-xBix)2Se3-based materials for optically tuneable photovoltaic applications. Towards chalcogenide narrow-bandgap devices

Quasi-1D chalcogenides have shown great promises in the development of emerging photovoltaic technologies. However, most quasi-1D semiconductors other than Sb2Se3 and Sb2S3 have been seldom investigated for energy generation applications. Indeed, cationic or anionic alloying strategies allow changing the bandgap of these materials, opening the door to the development of an extended range of chalcogenides with tuneable optical and electrical properties. In this work, Bi incorporation into the Sb2Se3 structure has been proved as an effective approach to modulate the bandgap between 0.1. In order to better understand the underlying mechanisms leading to the formation of (Sb1-xBix)2Se3, and thus design specific strategies to enhance its properties, thin films with different annealing time and temperature have been synthesized and characterized. Interestingly, it has been observed that Sb2Se3 and Bi2Se3 are formed first, with Bi melting at 300 ¿C and diffusing rapidly towards the surface of the film. At higher temperature, the binary compounds combine to form the solid solution, however as the dwell time increases, (Sb1-xBix)2Se3 decomposes again into Bi2Se3 and Sb. This study has shown that the material is essentially limited by compositional disorder and recombination via defects. Likewise, routes have been proposed to improve morphology and uniformity of the layer, achieving efficiencies higher than 1% for x > 0.2Postprint (published version

Challenges and improvement pathways to develop quasi-1D (Sb1-xBix)2Se3-based materials for optically tuneable photovoltaic applications. Towards chalcogenide narrow-bandgap devices

Quasi-1D chalcogenides have shown great promises in the development of emerging photovoltaic technologies. However, most quasi-1D semiconductors other than Sb2Se3 and Sb2S3 have been seldom investigated for energy generation applications. Indeed, cationic or anionic alloying strategies allow changing the bandgap of these materials, opening the door to the development of an extended range of chalcogenides with tuneable optical and electrical properties. In this work, Bi incorporation into the Sb2Se3 structure has been proved as an effective approach to modulate the bandgap between 0.1. In order to better understand the underlying mechanisms leading to the formation of (Sb1-xBix)2Se3, and thus design specific strategies to enhance its properties, thin films with different annealing time and temperature have been synthesized and characterized. Interestingly, it has been observed that Sb2Se3 and Bi2Se3 are formed first, with Bi melting at 300ºC and diffusing rapidly towards the surface of the film. At higher temperature, the binary compounds combine to form the solid solution, however as the dwell time increases, (Sb1-xBix)2Se3 decomposes again into Bi2Se3 and Sb. This study has shown that the material is essentially limited by compositional disorder and recombination via defects. Likewise, routes have been proposed to improve morphology and uniformity of the layer, achieving efficiencies higher than 1% for x>0.2

SbSeI and SbSeBr micro-columnar solar cells by a novel high pressure-based synthesis process

Van der Waals chalcogenides and chalcohalides have the potential to become the next thin film PV breakthrough, owing to the earth-abundancy and non-toxicity of their components, and their stability, high absorption coefficient and quasi-1D structure, which leads to enhanced electrical anisotropic properties when the material is oriented in a specific crystalline direction. However, quasi-1D semiconductors beyond Sb2(S,Se)3, such as SbSeX chalcohalides, have been scarcely investigated for energy generation applications, and rarely synthesised by physical vapor deposition methodologies, despite holding the promise of widening the bandgap range (opening the door to tandem or semi-transparent devices), and showing enticing new properties such as ferroelectric behaviour and defect-tolerant nature. In this work, SbSeI and SbSeBr micro-columnar solar cells have been obtained for the first time by an innovative methodology based on the selective halogenation of Sb2Se3 thin films at pressure above 1 atm. It is shown that by increasing the annealing temperature and pressure, the height and density of the micro-columnar structures grows monotonically, resulting in SbSeI single-crystal columns up to 30 µm, and tuneable morphology. In addition, solar cell prototypes with substrate configuration have shown remarkable Voc values above 550 mV and 1.8 eV bandgap.Peer ReviewedPostprint (published version