Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology.

While cadmium telluride and copper-indium-gallium-sulfide-selenide (CIGSSe) solar cells have either already surpassed (for CdTe) or reached (for CIGSSe) the 1 GW yr⁻¹ production level, highlighting the promise of these rapidly growing thin-film technologies, reliance on the heavy metal cadmium and scarce elements indium and tellurium has prompted concern about scalability towards the terawatt level. Despite recent advances in structurally related copper-zinc-tin-sulfide-selenide (CZTSSe) absorbers, in which indium from CIGSSe is replaced with more plentiful and lower cost zinc and tin, there is still a sizeable performance gap between the kesterite CZTSSe and the more mature CdTe and CIGSSe technologies. This review will discuss recent progress in the CZTSSe field, especially focusing on a direct comparison with analogous higher performing CIGSSe to probe the performance bottlenecks in Earth-abundant kesterite devices. Key limitations in the current generation of CZTSSe devices include a shortfall in open circuit voltage relative to the absorber band gap and secondarily a high series resistance, which contributes to a lower device fill factor. Understanding and addressing these performance issues should yield closer performance parity between CZTSSe and CdTe/CIGSSe absorbers and hopefully facilitate a successful launch of commercialization for the kesterite-based technology.

Dead zones in colloidal quantum dot photovoltaics: evidence and implications.

In order to fabricate photovoltaic (PV) cells incorporating light-trapping electrodes, flexible foil substrates, or more than one junction, illumination through the top-contact (i.e.: non-substrate) side of a photovoltaic device is desirable. We investigate the relative collection efficiency for illumination through the top vs. bottom of PbS colloidal quantum dot (CQD) PV devices. The external quantum efficiency spectra of FTO/TiO2/PbS CQD/ITO PV devices with various PbS layer thicknesses were measured for illumination through either the top (ITO) or bottom (FTO) contacts. By comparing the relative shapes and intensities of these spectra with those calculated from an estimation of the carrier generation profile and the internal quantum efficiency as a function of distance from the TiO2 interface in the devices, a substantial dead zone, where carrier extraction is dramatically reduced, is identified near the ITO top contact. The implications for device design, and possible means of avoiding the formation of such a dead zone, are discussed.

Quantum dot photovoltaics in the extreme quantum confinement regime: the surface-chemical origins of exceptional air- and light-stability.

We report colloidal quantum dot (CQDs) photovoltaics having a approximately 930 nm bandgap. The devices exhibit AM1.5G power conversion efficiencies in excess of 2%. Remarkably, the devices are stable in air under many tens of hours of solar illumination without the need for encapsulation. We explore herein the origins of this orders-of-magnitude improvement in air stability compared to larger PbS dots. We find that small and large dots form dramatically different oxidation products, with small dots forming lead sulfite primarily and large dots, lead sulfate. The lead sulfite produced on small dots results in shallow electron traps that are compatible with excellent device performance; whereas the sulfates formed on large dots lead to deep traps, midgap recombination, and consequent catastrophic loss of performance. We propose and offer evidence in support of an explanation based on the high rate of oxidation of sulfur-rich surfaces preponderant in highly faceted large-diameter PbS colloidal quantum dots.

Thiols passivate recombination centers in colloidal quantum dots leading to enhanced photovoltaic device efficiency.

The use of thiol-terminated ligands has recently been reported to enhance 10-fold the power conversion efficiency (PCE) of colloidal quantum dot (CQD) photovoltaic (PV) devices. We find herein that, in a representative amine-capped PbS colloidal quantum dot materials system, improved mobility following thiol treatment accounts for only a 1.4-fold increase in PCE. We then proceed to investigate the origins of the remainder of the quadrupling in PCE following thiol treatment. We find through measurements of photoluminescence quantum efficiency that exposure to thiols dramatically enhances photoluminescence in colloidal quantum dot films. The same molecules increase open-circuit voltage (V(oc)) from 0.28 to 0.43 V. Combined, these findings suggest that mid-gap states, which serve as recombination centers (lowering external quantum efficiency (EQE)) and metal-semiconductor junction interface states (lowering V(oc)), are substantially passivated using thiols. Through exposure to thiols, we improve EQE from 5 to 22% and, combined with the improvement in V(oc), improve power conversion efficiency to 2.6% under 76 mW/cm(2) at 1 microm wavelength. These findings are consistent with recent reports in photoconductive PbS CQD photodetectors that thiol exposure substantially removes deep (0.3 eV) electron traps, leaving only shallow (0.1 eV) traps.