David P. Ostrowski

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.

The Effects of Aggregation on Electronic and Optical Properties of Oligothiophene Particles

Solution processing of oligothiophene molecules is shown to produce a range of particles with distinct morphologies. Once isolated on a substrate, the optical and electronic properties of individual particles were studied. From polarized scanning confocal microscopy experiments, distinct particles that are identifiable by shape were shown to have similar emission spectra except in regard to the 0-0 vibronic band intensity. This suppression of the 0-0 vibronic band correlates to the amount of energetic disorder present in a weakly coupled H-aggregate. The studied particles ranged from moderate to almost complete suppression of the 0-0 vibronic band when compared to the emission spectrum of the isolated molecule in solution. All particles were found to have a high degree of geometric order (molecular alignment) as observed from the fluorescence dichroism (FD) values of around 0.7-0.8 for all the studied morphologies. The structural and electronic properties of the particles were investigated with Kelvin probe force microscopy (KPFM) to measure the local contact potential (LCP) difference, a quantity that is closely related to the differences in intermolecular charge distribution between the oligothiophene particles. The LCP was found to vary by as much as 70 mV between different oligothiophene particles and a trend was observed that correlated the LCP changes with the amount of energetic disorder present, as signified by the suppression of the 0-0 vibronic peak in the emission spectra. Combined polarized scanning confocal microscopy studies, along with KPFM measurements, help to provide fundamental insights into the role of morphology, molecular packing, and intermolecular charge distributions in oligiothiophene particles.

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.

Role of Crystallization in the Morphology of Polymer:Non-fullerene Acceptor Bulk Heterojunctions

Many high efficiency organic photovoltaics use fullerene-based acceptors despite their high production cost, weak optical absorption in the visible range, and limited synthetic variability of electronic and optical properties. To circumvent this deficiency, non-fullerene small-molecule acceptors have been developed that have good synthetic flexibility, allowing for precise tuning of optoelectronic properties, leading to enhanced absorption of the solar spectrum and increased open-circuit voltages (VOC). We examined the detailed morphology of bulk heterojunctions of poly(3-hexylthiophene) and the small-molecule acceptor HPI-BT to reveal structural changes that lead to improvements in the fill factor of solar cells upon thermal annealing. The kinetics of the phase transformation process of HPI-BT during thermal annealing were investigated through in situ grazing incidence wide-angle X-ray scattering studies, atomic force microscopy, and transmission electron microscopy. The HPI-BT acceptor crystallizes during film formation to form micron-sized domains embedded within the film center and a donor rich capping layer at the cathode interface reducing efficient charge extraction. Thermal annealing changes the surface composition and improves charge extraction. This study reveals the need for complementary methods to investigate the morphology of BHJs.

Thermal annealing affects vertical morphology, doping and defect density in BHJ OPV devices

We demonstrate that a post-annealing step results in enhanced open-circuit voltage (Voc) and fill factor (FF) and lower reverse saturation current (Js) that consequently increases the power conversion efficiency (PCE) of organic bulk-heterojunction (BHJ) devices by about 40 % as a result of better contact formation, as typically assumed. Although true, we show that additional device properties are affected as well. We found that annealing induces vertical phase segregation and consequently the enrichment of donor and acceptor materials at the correct electrical contact. In addition, a de-doping process and a decrease in defect density also take place and are the major causes for device improvement after post-annealing the OPV devices. Implications for OPV basic research and manufacturing are discussed.

High open circuit voltage organic photovoltaics: Minimizing energetic loss with a high band gap donor polymer and a small-molecule acceptor

Solution-processed, bulk-heterojunction Organic Photovoltaic (OPV) devices with a high Voc (up to 1.35 V) were fabricated with a high band gap electron-donor copolymer blended with a small-molecule electron-acceptor. The copolymer (PInCZ), based on carbazole and indolocarbazole monomers, posseses a deep lying HOMO (Highest Occupied Molecular Orbital) of -5.6 eV. Coupling this polymer with the small-molecule acceptor (HPI-BT), with a relatively shallow LUMO (Lowest Occupied Molecular Orbital) near -3.6 eV, resulted in an effective electronic band gap in the donor-acceptor pair of approximately 2.0 eV. This value, which is important in determining the maximum Voc attainable in the device, is substantially higher than the typical values found in OPV devices of ~1.0 - 1.5 eV. In the devices presented here, the thermodynamic loss in energy from the optical band gap compared to the Voc is ~41%, which is substantially lower than that commonly found in OPV materials of 50+%.