RESUMEN
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.
RESUMEN
Morphological effects on photovoltaic (PV) properties are studied through scanning photocurrent (PC) and photoluminescence (PL) microscopy of a solution processed, polymer blend PV device composed of PFB [poly(9,9'-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine] and F8BT [poly(9,9'-dioctylfluorene-co-benzothiadiazole]. As PFB and F8BT have unique absorbance bands, it is possible to selectively excite only F8BT (488 nm) or both PFB and F8BT (408 nm). Local voltage-dependent photocurrent (LVPC) measurements from particular regions of interest in the PV show that the diode characteristics between different morphologies are essentially the same, except in regard to the magnitude of PC generated. A local PL spectrum is measured simultaneously with PC generation at each pixel in the image maps. Through integration of the local PL spectrum over particular wavelength ranges, PL image maps are created of PFB-PL (435 to 475 nm), F8BT-PL (530 to 570 nm), exciplex-PL (620 to 685 nm) and total-PL (entire spectrum). These data allow direct correlation of PC generation with local chemical composition variations within the PV device. PL image maps show morphological variations on the order of 0.5 to 1 µm of alternating PFB-rich and F8BT-rich phases. While illuminating only F8BT (488 nm light), the PFB-rich phases produce the most PC, however, while illuminating both polymers but mostly PFB (408 nm light), the F8BT-rich phases produce the most PC. These results show that in the morphology where the light absorbing material is less concentrated, the PC generation is increased. Additionally, the exciplex-PL is found to not be a significant radiative loss mechanism of charge carriers for PC generation.
RESUMEN
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.
Asunto(s)
Cobre/química , Galio/química , Indio/química , Nanopartículas/química , Selenio/química , Energía Solar , Vidrio/química , TemperaturaRESUMEN
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 1.5â global (AMâ 1.5â 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.
Asunto(s)
Cobre/química , Suministros de Energía Eléctrica , Galio/química , Indio/química , Nanopartículas/química , Selenio/química , Energía Solar , Conductividad EléctricaRESUMEN
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.