Alexandre Crossay

Detecting ZnSe secondary phase in Cu2ZnSnSe4 by room temperature photoluminescence

Secondary phases, such as ZnSe, occur in Cu2ZnSnSe4 and can be detrimental to the resulting solar cell performance. Therefore, it is important to have simple tools to detect them. We introduce subband gap defect excitation room temperature photoluminescence of ZnSe as a practical and non-destructive method to discern the ZnSe secondary phase in the solar cell absorber. The PL is excited by the green emission of an Ar ion laser and is detected in the energy range of 1.2–1.3 eV. A clear spatial correlation with the ZnSe Raman signal confirms this attribution.

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

Continuous wave solid phase laser annealing of single-pot electrodeposited CuInSe2 thin films: Effects of Cu/In stoichiometry

CuInSe2 (CISe) is a prototype material for the I–III–VI chalcopyrites such as Cu(In,Ga)(S,Se)2 (CIGSSe) used as absorber layers in thin film photovoltaic cells. These thin film photovoltaic absorber layers are primarily synthesized by vacuum-based techniques in manufacturing. In this work, we investigate non-vacuum film synthesis by electrochemical deposition of CISe from a single bath followed by continuous wave laser annealing (CWLA) using a 1064 nm laser. We find that parameters exist for near-infrared CWLA which result in structural changes without melting and dewetting of the films. While Cu-poor samples show only about 40% reduction in the full width at half maximum (FWHM) of the respective x-ray diffraction (XRD) peaks, identically treated Cu-rich samples indicate a FWHM reduction of more than 70% in the XRD and Raman scattering data for irradiation at 50 W/cm2. This study demonstrates that an entirely solid-phase annealing path driven by intense illumination exists for chalopyrite phase formation ...

Pulsed and continuous wave solid phase laser annealing of electrodeposited CuInSe2 thin films

Cu(In,Ga)Se2 (CIGS) thin film photovoltaic absorber layers are primarily synthesized by vacuum based techniques at industrial scale. In this work, we investigate non-vacuum film synthesis by electrochemical deposition coupled with pulsed laser annealing (PLA) and or continuous wave laser annealing (CWLA) using 1064 nm laser. PLA results indicate that at high fluence (≥100 mJ/cm2) CuInSe2 films melt and dewet on both Mo and Cu substrates. In the submelt PLA regime (≤70 mJ/cm2) no change in XRD results is recorded. However CWLA at 50 W/cm2 for up to 45 s does not result in melting or dewetting of the film. XRD and Raman data indicate more than 80% reduction in full width at half maximum (FWHM) in their respective main peaks for annealing time of 15 s or more. No other secondary phases are observed in XRD or Raman spectrum. These results might help us in setting up the foundation for processing CIGS through an entirely non-vacuum process.

Understanding quaternary compound Cu2ZnSnSe4 synthesis by microscopic scale analyses at an identical location

The synthesis of multinary compound films from layered precursors is only partially understood. Identical location microscopy resolves the multi-step synthesis of Cu2ZnSnSe4 from metallic stacks on the micron-scale. Large scale metal alloying and the seemingly illogical observation that ZnSe segregates preferentially on locations previously poor of zinc are revealed.