Search

Cadmium-free buffer layers deposited by a dry vacuum process are mandatory for low-cost and environmentally friendly Cu(In1-xGax)Se2 (CIGS) photovoltaic in-line production. Zn(O,S) has been identified as an alternative to the chemical bath deposited CdS buffer layer, providing comparable power conversion efficiencies. Recently, a significant efficiency enhancement has been reported for sputtered Zn(O,S) buffers after an annealing treatment of the complete solar cell stack; the enhancement was attributed to interdiffusion at the CIGS/Zn(O,S) interface, resulting in wide-gap ZnSO4 islands formation and reduced interface defects. Here, we exclude interdiffusion or island formation at the absorber/buffer interface after annealing up to 200 °C using high-resolution scanning transmission electron microscopy (HR-STEM) and energy-dispersive X-ray spectroscopy (EDX). Interestingly, HR-STEM imaging reveals an epitaxial relationship between a part of the Zn(O,S) buffer layer grains and the CIGS grains induced by annealing at such a low temperature. This alteration of the CIGS/buffer interface is expected to lead to a lower density of interface defects, and could explain the efficiency enhancement observed upon annealing the solar cell stack, although other causes cannot be excluded.

Micro-concentrator solar cells enable higher power conversion efficiencies and material savings when compared to large-area non-concentrated solar cells. In this study, we use materials-efficient area-selective electrodeposition of the metallic elements, coupled with selenium reactive annealing, to form Cu(In,Ga)Se2 semiconductor absorber layers in patterned microelectrode arrays. This process achieves significant material savings of the low-abundance elements. The resulting copper-poor micro-absorber layers’ composition and homogeneity depend on the deposition charge, where higher charge leads to greater inhomogeneity in the Cu/In ratio and to a patchy presence of a CuIn5Se8 OVC phase. Photovoltaic devices show open-circuit voltages of up to 525 mV under a concentration factor of 18 ×, which is larger than other reported Cu(In,Ga)Se2 micro-solar cells fabricated by materials-efficient methods. Furthermore, a single micro-solar cell device, measured under light concentration, displayed a power conversion efficiency of 5% under a concentration factor of 33 ×. These results show the potential of the presented method to assemble micro-concentrator photovoltaic devices, which operate at higher efficiencies while using light concentration.

International audience; A promising approach of making high quality contacts on semiconductors is a silicidation (for silicon) or germanidation (for germanium) annealing process, where the metal enters the semiconductor and creates a low resistance intermetallic phase. In a nanowire, this process allows one to fabricate axial heterostructures with dimensions depending only on the control and understanding of the thermally induced solid-state reaction. In this work, we present the first observation of both germanium and copper diffusion in opposite directions during the solid-state reaction of Cu contacts on Ge nanowires using in situ Joule heating in a transmission electron microscope. The in situ observations allow us to follow the reaction in real time with nanometer spatial resolution. We follow the advancement of the reaction interface over time, which gives precious information on the kinetics of this reaction. We combine the kinetic study with ex situ characterization using model-based energy dispersive X-ray spectroscopy (EDX) indicating that both Ge and Cu diffuse at the surface of the created Cu3Ge segment and the reaction rate is limited by Ge surface diffusion at temperatures between 360 and 600 °C. During the reaction, germanide crystals typically protrude from the reacted NW part. However, their formation can be avoided using a shell around the initial Ge NW. Ha direct Joule heating experiments show slower reaction speeds indicating that the reaction can be initiated at lower temperatures. Moreover, they allow combining electrical measurements and heating in a single contacting scheme, rendering the Cu–Ge NW system promising for applications where very abrupt contacts and a perfectly controlled size of the semiconducting region is required. Clearly, in situ TEM is a powerful technique to better understand the reaction kinetics and mechanism of metal–semiconductor phase formation.