Dissertations and theses : Doctoral thesis
Physical, chemical, mathematical & earth Sciences : Physics
Physics and Materials Science
Lomuscio, Alberto mailto [University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit >]
University of Luxembourg, ​Esch-sur-Alzette, ​​Luxembourg
Docteur en Physique
Siebentritt, Susanne mailto
[en] Photoluminescence ; Defects ; Solar cells ; Chalcopyrites ; CuInS2 ; QFLS
[en] Pure-sulphide Cu(In,Ga)S2 solar cells have reached certified power conversion efficiency as high as 15.5 %. While this record performance has been achieved by growing the semiconducting absorber at very high temperature with a copper deficient composition, all other previous records were based on chalcopyrite films deposited under Cu excess. Still, this world record is far from the theoretical power conversion achievable in single junction solar cell for this semiconductor (about 30 %), which has a tunable band gap between 1.5 and 2.4 eV.
This thesis aims to gain insight into the optoelectronic properties of this semiconductor, particularly CuInS2, looking at their variation as a function of the deposition temperature and of the absorber composition. The investigations are carried out mainly by photoluminescence (PL) spectroscopy, which allows to measure the quasi Fermi level splitting (QFLS), that is an upper limit of the maximum open circuit voltage (VOC) an absorber is capable of. PL spectroscopy is used to get insights onto the electronic defects as well, both the shallow ones, which contribute to the doping, and the deep ones, which enhance non-radiative recombination.
By increasing the Cu content in the as-grown compositions, the morphology and microstructure of the thin films improve, as they show larger grains and less structural defects than films deposited with Cu deficiency. The composition affects the QFLS as well, which is significantly higher for sample deposited under Cu excess, in contrast to the observations in selenide chalcopyrite. The increment of the process temperature leads to an improvement of the QFLS too, although absorbers grown in Cu deficiency are less influenced, likely because of a lower sodium content in the high-temperature glass used as substrate. The QFLS increase correlates with the lowering of a deep defect related band, which manifests itself with a peak maximum at around 0.8 eV in room temperature PL spectra.
In literature, the low efficiencies exhibited by Cu(In,Ga)S2–based solar cells are often attributed to interface problems at the p-n junction, i.e. at the absorber-buffer layer interface. In this work, the comparison of the QFLS and VOC of pure sulphides CIGS with those measured on selenides clearly points out that the lower efficiencies exhibited by the former are caused also by the intrinsic lower optoelectronic quality of Cu(In,Ga)S2 films.
To shed light on the electronic structure, high quality CuInS2 films are deeply investigated by means of low temperature PL. Four shallow defects are detected: one shallow donor at about 30 meV from the conduction band and three shallow acceptors at about 105, 145 and 170 meV from the valence band. The first of these acceptors dominates the band edge luminescence of sample grown with composition close to the stoichiometry, whereas the second deeper acceptor is characteristic of absorbers deposited in Cu rich regime. The deepest of these acceptors seems to be present over a wide range of compositions, although its luminescence is observable only for slight Cu-poor samples with sodium incorporation during the deposition. The quality of the examined films allows the observations of phonon coupling of these shallow defects for the first time in this semiconductor. All these observations on shallow defects and their phonon coupling behaviour allowed to revise the defect model for this semiconductor.
The findings of this thesis reveal the strong similarity of the shallow defects structure with selenium based compounds. On the other hand, the presence of deep defects in CuInS2 strongly limits the optoelectronic quality of the bulk material, causing the gap in power conversion efficiencies compared to low-band gap Cu(In,Ga)Se2 solar cells, which show efficiencies above 23%.
Laboratory for Photovoltaics
Fonds National de la Recherche - FnR
Researchers ; Professionals

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