Ondrej Dyck

Perovskite Solar Cells with Near 100% Internal Quantum Efficiency Based on Large Single Crystalline Grains and Vertical Bulk Heterojunctions

Imperfections in organometal halide perovskite films such as grain boundaries (GBs), defects, and traps detrimentally cause significant nonradiative recombination energy loss and decreased power conversion efficiency (PCE) in solar cells. Here, a simple layer-by-layer fabrication process based on air exposure followed by thermal annealing is reported to grow perovskite films with large, single-crystal grains and vertically oriented GBs. The hole-transport medium Spiro-OMeTAD is then infiltrated into the GBs to form vertically aligned bulk heterojunctions. Due to the space-charge regions in the vicinity of GBs, the nonradiative recombination in GBs is significantly suppressed. The GBs become active carrier collection channels. Thus, the internal quantum efficiencies of the devices approach 100% in the visible spectrum range. The optimized cells yield an average PCE of 16.3 ± 0.9%, comparable to the best solution-processed perovskite devices, establishing them as important alternatives to growing ideal single crystal thin films in the pursuit toward theoretical maximum PCE with industrially realistic processing techniques.

Synthesis of Millimeter-Size Hexagon-Shaped Graphene Single Crystals on Resolidified Copper

We present a facile method to grow millimeter-size, hexagon-shaped, monolayer, single-crystal graphene domains on commercial metal foils. After a brief in situ treatment, namely, melting and subsequent resolidification of copper at atmospheric pressure, a smooth surface is obtained, resulting in the low nucleation density necessary for the growth of large-size single-crystal graphene domains. Comparison with other pretreatment methods reveals the importance of copper surface morphology and the critical role of the melting-resolidification pretreatment. The effect of important growth process parameters is also studied to determine their roles in achieving low nucleation density. Insight into the growth mechanism has thus been gained. Raman spectroscopy and selected area electron diffraction confirm that the synthesized millimeter-size graphene domains are high-quality monolayer single crystals with zigzag edge terminations.

Universal Formation of Compositionally Graded Bulk Heterojunction for Efficiency Enhancement in Organic Photovoltaics

A universal method is reported to form graded bulk heterojunction (BHJ) organic photovoltaic devices (OPVs) by a simple solvent-fluxing process. Donors are enriched at the anode and acceptors are enriched at cathode side, matching the gradient electron and hole current across the film. Efficiency enhancements by 15-50% are achieved for all BHJ systems tested compared with the optimized regular BHJ OPVs.

Guided crystallization of P3HT in ternary blend solar cell based on P3HT:PCPDTBT:PCBM

To mimic the performance of the tandem solar cells, ternary blend solar cells with a single active layer of P3HT:PCPDTBT:PC61BM were cast from chlorobenzene and thermally annealed. By varying blending ratio, thermal annealing time and P3HT molecular weight, the device performance was enhanced relative to the binary references. To understand this, the morphology of the active layer was studied using hard and soft X-ray scattering methods in concert with bright field and energy resolved transmission electron microscopies. We found that the phase separation of the amorphous PCPDTBT and P3HT guided the formation of P3HT fibrils, resulting in a unique multi-length-scale morphology. This morphology consisted of bundles of well-defined P3HT fibrils, forming a network, imbedded in an amorphous mixture of the PCBM, PCPDTBT and P3HT. The two polymers acted independently in their specific photoactive ranges, and the sensitization of PCPDTBT benefited the cascade charge transfer. This multi-length-scale morphology was linked to the improved device performance of P3HT:PCPDTBT:PC61BM and the photophysics of the active layer.

Placing single atoms in graphene with a scanning transmission electron microscope

We demonstrate that the sub-atomically focused beam of a scanning transmission electron microscope (STEM) can be used to controllably manipulate individual dopant atoms in a 2D graphene lattice. We demonstrate the manipulation of adsorbed source materials and the graphene lattice with the electron beam such that individual vacancy defects can be controllably passivated by Si substitutional atoms. We further demonstrate that these Si defects may be directed through the lattice via e-beam control or modified (as yet, uncontrollably) to form new defects which can incorporate new atoms into the graphene lattice. These studies demonstrate the potential of STEM for atom-by-atom nanofabrication and fundamental studies of chemical reactions in 2D materials on the atomic level.We employ the sub-atomically focused beam of a scanning transmission electron microscope (STEM) to introduce and controllably manipulate individual dopant atoms in a 2D graphene lattice. The electron beam is used to create defects and subsequently sputter adsorbed source materials into the graphene lattice such that individual vacancy defects are controllably passivated by Si substitutional atoms. We further document that Si point defects may be directed through the lattice via e-beam control or modified (as yet, uncontrollably) to form new defects which can incorporate new atoms into the graphene lattice. These studies demonstrate the potential of STEM for atom-by-atom nanofabrication and fundamental studies of chemical reactions in 2D materials on the atomic level.

The impact of selective solvents on the evolution of structure and function in solvent annealed organic photovoltaics

This study examines the development of structure and performance in an organic photovoltaic (OPV) thin film comprised of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). Specifically, the influence of P3HT and PCBM solubility in the solvents utilized for vapor annealing on the morphological properties and OPV performance of the resultant active layer is examined. The evolution of P3HT crystallinity as well as the growth of PCBM aggregates in the solvent annealed thin films were examined by Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), Atomic Force Microscopy (AFM), and Energy Filtered Transmission Electron Microscopy (EFTEM). It is shown that P3HT crystallinity increases initially, then decreases with time for solvents that have a finite P3HT solubility. Alternatively, PCBM aggregates grow continuously with SVA, but are modulated by the PCBM solubility. High P3HT crystallinity and moderate PCBM phase separation correlates to improved power conversion efficiency (PCE). Hence, the relative P3HT and PCBM solubility plays a crucial role in choosing the best SVA time of different annealing solvents. Specifically, for samples annealed using solvents that prefer P3HT, PCE benefits from further SVA after the peak P3HT crystallinity time, which is ascribed to additional PCBM phase separation. On the other hand, solvents that prefer PCBM induce excess PCBM phase separation at longer SVA times, which limits exciton dissociation and PCE. EFTEM cross section images indicate that PCBM is distributed toward the bottom of the film, whereas SVA in a solvent with high PCBM solubility may induce PCBM to segregate towards the air surface, which benefits charge transport processes by preventing electron–hole recombination.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

Mitigating e-beam-induced hydrocarbon deposition on graphene for atomic-scale scanning transmission electron microscopy studies

Chemical vapor deposition (CVD) grown graphene used in (scanning) transmission electron microscopy [(S)TEM] studies must undergo a careful transfer of the one-atom-thick membrane from the growth surface (typically a Cu foil) to the TEM grid. During this transfer process, the graphene invariably becomes contaminated with foreign materials. This contamination proves to be very problematic in the (S)TEM because often >95% of the graphene is obscured, and imaging of the pristine areas results in e-beam-induced hydrocarbon deposition which further acts to obscure the desired imaging area. In this article, the authors examine two cleaning techniques for CVD grown graphene that mitigate both aspects of the contamination problem: visible contamination covering the graphene, and “invisible” contamination that deposits onto the graphene under e-beam irradiation. The visible contamination may be removed quickly by a rapid thermal annealing to 1200 °C in situ and the invisible e-beam-deposited contamination may be removed through an Ar/O2 annealing procedure prior to imaging in the (S)TEM.Chemical vapor deposition (CVD) grown graphene used in (scanning) transmission electron microscopy [(S)TEM] studies must undergo a careful transfer of the one-atom-thick membrane from the growth surface (typically a Cu foil) to the TEM grid. During this transfer process, the graphene invariably becomes contaminated with foreign materials. This contamination proves to be very problematic in the (S)TEM because often >95% of the graphene is obscured, and imaging of the pristine areas results in e-beam-induced hydrocarbon deposition which further acts to obscure the desired imaging area. In this article, the authors examine two cleaning techniques for CVD grown graphene that mitigate both aspects of the contamination problem: visible contamination covering the graphene, and “invisible” contamination that deposits onto the graphene under e-beam irradiation. The visible contamination may be removed quickly by a rapid thermal annealing to 1200 °C in situ and the invisible e-beam-deposited contamination may be re...

Exciton emission from hybrid organic and plasmonic polytype InP nanowire heterostructures

We investigate the emission of excitons in bare, hybrid organic, and metal coated polytype wurtzite/zincblende (WZ/ZB) InP nanowire (NW) heterostructures by intensity- and temperature-dependent time-integrated (TI) and time-resolved (TR) photoluminescence (PL). TI PL measurements at 20 K reveal two strong emission bands at ?1.48 and ?1.44 eV that are attributed to non-thermalized weakly and deeply localized indirect WZ/ZB excitons due to randomly distributed short WZ and ZB segments. The PL yield of both bands increases when the NWs are covered with an Alq3 layer which is attributed to surface charge passivation. In metal coated NWs the weakly localized indirect WZ/ZB exciton emission is significantly reduced while the strongly localized indirect WZ/ZB band is less affected. The observed PL quenching is attributed to radiationless F?rster energy-transfer from NW excitons to plasmon oscillations in the deposited metal. TR PL investigations support this interpretation revealing enhanced PL lifetimes in Alq3 coated NWs compared to uncovered NWs. The lifetime of weakly trapped indirect excitons is shortest in metal coated NWs due to F?rster energy-transfer while the dynamics of strongly localized indirect WZ/ZB excitons is less affected because of the small dipole-moment of these transitions.

DC electric field induced phase array self-assembly of Au nanoparticles

In this work we report the discovery of phase array self-assembly, a new way to spontaneously make periodic arrangements of metal nanoparticles. An initially random arrangement of gold (Au) or silver (Ag) nanoparticles on SiO2/Si substrates was irradiated with linearly polarized (P) laser light in the presence of a dc electric (E) field applied to the insulating substrate. For E fields parallel to the laser polarization (E||P), the resulting periodic ordering was single-crystal like with extremely low defect density and covered large macroscopic areas. The E field appears to be modifying the phase between radiation scattered by the individual nanoparticles thus leading to enhanced interference effects. While phase array behavior is widely known in antenna technology, this is the first evidence that it can also aid in nanoscale self-assembly. These results provide a simple way to produce periodic metal nanoparticles over large areas.