C. Jackson Stolle

CuInSe2 Quantum Dot Solar Cells with High Open-Circuit Voltage.

CuInSe2 (CISe) quantum dots (QDs) were synthesized with tunable size from less than 2 to 7 nm diameter. Nanocrystals were made using a secondary phosphine selenide as the Se source, which, compared to tertiary phosphine selenide precursors, was found to provide higher product yields and smaller nanocrystals that elicit quantum confinement with a size-dependent optical gap. Photovoltaic devices fabricated from spray-cast CISe QD films exhibited large, size-dependent, open-circuit voltages, up to 849 mV for absorber films with a 1.46 eV optical gap, suggesting that midgap trapping does not dominate the performance of these CISe QD solar cells.

Multiexciton Solar Cells of CuInSe2 Nanocrystals

Peak external quantum efficiencies (EQEs) of just over 120% were observed in photovoltaic (PV) devices of CuInSe2 nanocrystals prepared with a photonic curing process. The extraction of more than one electron/hole pair as a result of the absorption of a single photon can occur if multiple excitons are generated and extracted. Multiexciton generation (MEG) in the nanocrystal films was substantiated by transient absorption spectroscopy. We propose that photonic curing leads to sufficient electronic coupling between nanocrystals to enable multiexciton extraction under typical solar illumination conditions. Under low light conditions, however, the EQE drops significantly, indicating that photonic curing-induced ligand desorption creates a significant amount of traps in the film that limit the overall power conversion efficiency of the device.

Comparison of the photovoltaic response of oleylamine and inorganic ligand-capped CuInSe2 nanocrystals.

Thin film photovoltaic devices (PVs) were fabricated with CuInSe(2) (CIS) nanocrystals capped with either oleylamine, inorganic metal chalcogenide-hydrazinium complexes (MCC), or S(2-), HS(-), and OH(-). A CIS nanocrystal layer deposited from solvent-based inks without high temperature processing served as the active light-absorbing material in the devices. The MCC ligand-capped CIS nanocrystal PVs exhibited power conversion efficiency under AM1.5 illumination (1.7%) comparable to the oleylamine-capped CIS nanocrystals (1.6%), but with significantly thinner absorber layers. S(2-)-capped CIS nanocrystals could be deposited from aqueous dispersions, but exhibited lower photovoltaic performance.

Copper indium gallium selenide (CIGS) photovoltaic devices made using multistep selenization of nanocrystal films.

The power conversion efficiency of photovoltaic devices made with ink-deposited Cu(InxGa1-x)Se2 (CIGS) nanocrystal layers can be enhanced by sintering the nanocrystals with a high temperature selenization process. This process, however, can be challenging to control. Here, we report that ink deposition followed by annealing under inert gas and then selenization can provide better control over CIGS nanocrystal sintering and yield generally improved device efficiency. Annealing under argon at 525 °C removes organic ligands and diffuses sodium from the underlying soda lime glass into the Mo back contact to improve the rate and quality of nanocrystal sintering during selenization at 500 °C. Shorter selenization time alleviates excessive MoSe2 formation at the Mo back contact that leads to film delamination, which in turn enables multiple cycles of nanocrystal deposition and selenization to create thicker, more uniform absorber films. Devices with power conversion efficiency greater than 7% are fabricated using the multiple step nanocrystal deposition and sintering process.

Efficient Carrier Multiplication in Colloidal CuInSe2 Nanocrystals

Transient absorption spectroscopy (TAS) was used to study carrier multiplication (CM) (also called multiexciton generation (MEG)) in solvent-dispersed colloidal CuInSe2 nanocrystals with diameters as small as 4.5 nm. Size-dependent carrier cooling rates, absorption cross sections, and Auger lifetimes were also determined. The energy threshold for CM in the CuInSe2 nanocrystals was found to be 2.4 ± 0.2 times the nanocrystal energy gap (Eg) and the CM efficiency was 36 ± 6% per unit Eg. This is similar to other types of nanocrystal quantum dot materials.

Influence of Composition on the Performance of Sintered Cu(In,Ga)Se2 Nanocrystal Thin‐Film Photovoltaic Devices

Thin-film photovoltaic devices (PVs) were prepared by selenization using oleylamine-capped Cu(In,Ga)Se2 (CIGS) nanocrystals sintered at a high temperature (>500 °C) under Se vapor. The device performance varied significantly with [Ga]/[In+Ga] content in the nanocrystals. The highest power conversion efficiency (PCE) observed in the devices studied was 5.1 % under air mass 1.5 global (AM 1.5 G) illumination, obtained with [Ga]/[In+Ga]=0.32. The variation in PCE with composition is partly a result of bandgap tuning and optimization, but the main influence of nanocrystal composition appeared to be on the quality of the sintered films. The [Cu]/[In+Ga] content was found to be strongly influenced by the [Ga]/[In+Ga] concentration, which appears to be correlated with the morphology of the sintered film. For this reason, only small changes in the [Ga]/[In+Ga] content resulted in significant variations in device efficiency.

Photonic curing of ligand-capped CuInSe 2 nanocrystal films

CuInSe2 nanocrystals capped with oleylamine or chalcogenidometallate (ChaM) clusters, also known as metal chalcogenide complexes (MCC), were deposited from solution and sintered by photonic curing with a high intensity pulsed white light source. Oleylamine-capped nanocrystals sinter via melting and resolidification, regardless of pulse power used in the curing process, resulting in non-uniform layers with significant regions of exposed back contact. ChaM-capped nanocrystals on the other hand could be sintered at significantly lower pulse power to avoid melting and retain layer integrity. At higher pulse power, ChaM-capped nanocrystals melt but adhere more uniformLy to the substrate.