Grain-Boundary Structural Relaxation in Sb2Se3{\mathrm{Sb}}_{2}{\mathrm{Se}}_{3} Thin-Film Photovoltaics

Grain boundaries play an important role in the efficiency of thin-film photovoltaics, where the absorber layer is invariably polycrystalline. Density-functional-theory simulations have previously identified a “self-healing” mechanism in Sb2Se3 that passivates the grain boundaries. During “self-healing,” extensive structural relaxation at the grain boundary removes the band-gap electronic defect states that give rise to high carrier recombination rates. In this work, lattice imaging in a transmission electron microscope is used to uncover evidence for the theoretically proposed structural relaxation in Sb2Se3. The strain measured along the [010] crystal direction is found to be dependent on the nature of the grain-boundary plane. For a (010) grain boundary, the strain and structural relaxation is minimal, since no covalent bonds are broken by termination of the grain. On the other hand, strains of up to approximately 4% extending approximately 2 nm into the grain interior are observed for a (041) grain boundary, where grain termination results in significant structural relaxation due to the ideal atomic coordination being disrupted. These results are consistent with theory and suggest that Sb2Se3 may have a high level of grain-boundary-defect tolerance

Crystal structure and anti-site boundary defect characterisation of Cu2ZnSnSe4

The crystal structure identification of the photovoltaic material Cu2ZnSnSe4 (CZTSe) is challenging due to the distinguishing feature between the two polymorphs, kesterite and stannite, being the arrangement of Cu and Zn ions. Here an energy dispersive X-ray (EDX) technique, based on electron beam channeling along specific crystallographic planes in a transmission electron microscope (TEM), is used to identify the structure. Regions a few 100 nm in size can be analysed using this method, unlike neutron or anomalous X-ray scattering. The parent crystal structure of CZTSe, annealed on either side of the order–disorder transition temperature, was correctly identified as being kesterite. The presence of 1/2[110] (001) and 1/4[201] (101) anti-site boundaries (ASBs) has also been investigated. The density of ASBs is higher above the transition temperature, due to a smaller energy penalty for disordering on the 2c and 2d Wyckoff sites. A nearest neighbour cation analysis predicted the 1/2[110] (001) ASB to have the lowest formation energy. From density functional theory (DFT) simulations the 1/2[110] (001) ASB energy is only 43 mJ m−2 and furthermore it is not a recombination site or current blocking layer, so that photovoltaic device performance is not significantly degraded

Structure and electronic properties of domain walls and stacking fault defects in prospective photoferroic materials bournonite and enargite

Bournonite (CuPbSbS3) and enargite (Cu3AsS4) have recently been used as absorber layers in thin-film photovoltaic devices due to their ideal bandgap and ferroelectric properties. An understanding of the ferroelectric domain structure in these materials is required so that the benefits of the internal depolarizing electric fields can be fully exploited. Here, the atomic structure and electronic properties of domain walls (DWs) are elucidated through a combined aberration-corrected scanning transmission electron microscopy and density functional theory study. ∼90° and 180° DWs are observed in bournonite. As the 180° DW is charge neutral, it cannot contribute to the anomalous photovoltaic effect that leads to high open circuit voltages. The ∼90° DW shows a slight offset across the boundary, but the contributions of this to the anomalous photovoltaic effect are negligible. The DWs are also electrically passive, i.e., they do not result in significant recombination and do not block charge carrier transport. A high density of stacking faults (SF) was, however, observed in enargite. The SFs have a large number of defect states within the bandgap, which would lower the device efficiency through Shockley–Read–Hall recombination

Beyond inequality? A case study of progression, achievements and experiences of health and care workers in higher education, 2005–2011

During the first decade of the new millennium, the New Labour government promoted a discourse of inclusion in health and care work in two central ways:• A restructured career ladder was introduced with the aim of offering advancement based on ability.• The Foundation degree was introduced, as an attempt to open up access to health education in higher education (HE).This paper focuses on the latter, analysing the progression statistics of all entrants to one Foundation degree (at a research-intensive university) over six years. Two groups of students are discussed: those who attained honours degrees and professional qualifications (30% of all who continued) and those who left with no qualifications (19% of all entrants).In order to move beyond typologies that seek to correlate personal characteristics with the likelihood to achieve, we reflect on the contextual and social factors reported by students. Interviews reinforce the importance of peer support and the prospect of a professional career. The dataset examined here would suggest that the range of student voices needs to be attended to with greater sensitivity if the plurality of student perspectives and needs are not to be obscured. The data here enables a more profound consideration of what inclusion could mean