KEYWORDS: Quantum wells, Perovskite, Nanostructures, Thin films, Crystals, X-rays, X-ray characterization, Thin film solar cells, Thin film devices, Solar energy
Controlling the formation, size distribution and orientation of quantum wells (QWs) in layered hybrid perovskite (LHP) thin films is foundational to their optoelectronic device applications. These applications require exquisite control of energy and charge transport which tend to be highly anisotropic in low-dimensional phases in LHP thin films. Here, we combine a powerful suite of multimodal in situ characterizations to elucidate the precise solution-to-solid conversion of the sol into the LHP thin film. We identify, for the first time, the presence of oriented colloidal transient nanostructures during spin coating well before the onset of crystallization of phases.
Recent advancements in the field of organic electronics and bioelectronics have focused on the processing of PEDOT:PSS with ionic additives to promote high electrical conductivity and device performance. The combination of excellent electrical properties and tunable structure are increasingly attractive, however, the mechanism responsible for these properties, specifically from a solution-phase self-assembly perspective, is unknown. Herein, we reveal how solution-phase self-assembly of PEDOT:PSS with ionic additives leads to multiscale ordering which influences thin film microstructure, electronic properties, enables new additive manufacturing modalities, and applications in aqueous environments.
Anomalous properties such as operational instability and photocurrent hysteresis in perovskite-based devices present a major obstacle to their future commercialization. Halide ion/defect migration has been widely accepted as one of the main mechanisms behind these limiting properties, but a definitive explanation of this relationship has remained elusive. Here, we present a quantitative multi-scale diffusion framework that fully describes halide diffusion in polycrystalline metal halide perovskites (MHPs). By using time-of-flight secondary ion mass spectroscopy (ToF-SIMS) technique we could simultaneously monitor both the fast grain boundary (GB) diffusivity and three to four orders of magnitude slower volume/bulk diffusivity. Our framework reveals an inverse relationship between the activation energies of GB (EGB) and volume (EV) diffusions, such that MHPs (such as MAPbI3) with a larger EV also possess a smaller EGB. Importantly, this relationship explains some of the most conflicting observations in the literature, namely that MHPs with improved stability typically exhibit reduced hysteresis, thanks to the simultaneous existence of small volume and large GB halide diffusivities, respectively, pointing us to propose a model of grain boundary “strength”. This nontrivial relation between volume and GB halide diffusivities is derived from a wide range of MHP systems, including MA- and FA-based iodide and bromide perovskites. Even when GB passivation approaches are used, GB diffusivity increases reducing hysteresis at the expense of volume diffusion, which enhances stability. The quantitative elucidation of multiscale halide diffusion in polycrystalline MHPs provides an important path toward addressing these outstanding issues.
The vast chemical and processing universe of emerging halide perovskite materials can be overwhelming to traditional research practices. The sheer scale of the design problem and the emergent nature of many phenomena, including highly nonequilibrium thin film processing, complex solution-to-solid phase transformation can be overwhelming for traditional trial-and-error investigations. Solving such a complex problem would benefit from a robot-in-the-loop strategy that can accelerate many of the manual tasks as well as reduce cost and waste generation and support implementation of artificial intelligence. We present the RoboMapper, our recent effort to leverage robotic automation towards accelerating parameter space exploration and establishment of formulation-structure-property relationships with orders of magnitude enhancement in research efficiency. We will demonstrate formulation, printing and characterization of halide perovskites towards the aim of accelerating research workflows.
Tandem structure provides a practical way to realize high efficiency organic photovoltaic (OPV) cells due to the limited optical absorption in organic semiconductors and tandem cells can be used to extend the wavelength coverage of the solar spectrum for light harvesting. The interconnecting layer (ICL) between subcells in a tandem solar cell plays a critical role in the reproducibility and the performance of tandem devices, and the processability of the ICL in a tandem cell has been a challenge. In this work we report on the fabrication of highly reproducible high efficiency tandem cells by employing a commercially available material, PEDOT:PSS HTL Solar (HSolar), as the hole transporting material used for the ICL. Comparing with the conventional PEDOT:PSS Al 4083, HSolar offers a better wettability on the underlying non-fullerene photoactive layers, resulting in better charge extraction properties of the ICL. When FTAZ:IT-M and PTB7-Th:IEICO-4F are used as the front cell and the back cells to fabricate the tandem solar cells, a power conversion efficiency (PCE) of 14.7% is achieved. To validate the processability of these tandem cells, three other research groups have successfully fabricated tandem cells using the same recipe and the highest PCE obtained is 16.1%. With further development of donor polymers and device optimization, our device simulation results show that a PCE < 22% can be realized in tandem cells in the near future.
Mixed halide, mixed cation lead perovskite films have been demonstrated to benefit tremendously from the addition of Cs and Rb into the perovskite formulation, resulting in high performance, enhanced reproducibility and stability. However, the root cause of these effects in these complicated systems is not well understood. We address the above challenge by tracking in situ the solidification of perovskite precursors during solution-casting using time-resolved grazing incidence wide-angle X-ray scattering (GIWAXS). In doing so, we can directly link the formation or suppression of different crystalline phases to the presence of Cs and/or Rb. In the absence of these elements, the multi-component perovskite film is inherently unstable, phase segregating into a solvated MAI-rich phase and a FABr-rich phase. Adding even one of the two (Cs or Rb) is shown to alter the solidification quite dramatically, promoting different solidification pathways. Importantly, the addition of both components in the optimal ratio can drastically suppress phase segregation and promotes the spontaneous formation of the desired perovskite phase. This result is also confirmed by elemental mapping of organic cations (FA+, MA+) and halide anions (I-, Br-) via time-of-flight secondary ion mass spectroscopy (ToF-SIMS). Perovskite precursors with an optimal combination of additives (7% Cs, 3% Rb) result in solar cells with 20.1% power conversion efficiency (PCE), outperforming formulation excluding Cs and Rb (PCE=14.6%). We propose that the synergistic effect is due to the collective benefits of Cs and Rb on the formation kinetics of the perovskite phase, and on the halides redistribution throughout the film. Importantly, our study points to new design rules for tuning the crystallization pathway of multi-component hybrid perovskites.
KEYWORDS: Interfaces, Heterojunctions, Solar cells, Spectroscopy, Scanning tunneling microscopy, Fullerenes, Annealing, Polymers, Nanomaterials, Electron transport
The nanoscale organization and corresponding electronic properties of a photoactive donor-acceptor blend layers based on regioregular poly (3-hexylthiophene) (RR-P3HT) donor with fullerene and non-fullerene acceptors on Au(111) substrate has been studied using scanning tunneling microscopy and spectroscopy (STM/STS). Subsequent to annealing treatment, STM topography and dI⁄dV images are observed as a combination of phase-separated donor-rich, acceptor-rich, and mixed donor-acceptor domains. This technique permits to explore simultaneously the quantitative linkage between the nanoscale morphologies and corresponding local electronic properties. We determine the HOMO and LUMO-edges at the individual domains and interfacial band alignments of the donor-acceptor interface. We have observed a noteworthy deeper HOMO energy of RR-P3HT in mixed-region associated primarily with the degree of disorder-induced band gap widening of the polymer and donor:acceptor intermolecular interactions. Similarly, LUMO of the acceptor in the mixed region is also raised due to intermolecular interaction. These energetic difference in the mixed phase is likely to be responsible for the reduced recombination in bulk heterojunction (BHJ). Hence, this characterization provides nanoscale insight to the annealing-induced morphological organization and corresponding local electronic properties account for an impressive increase of the charge generation, transport and corresponding device performance of the BHJ solar cells.
Organic electronic materials are desirable due to facile and low-cost manufacturing through solution deposition. However, the inherit difficulties of reproducibility and solvent compatibility, as well as the hazards associated with the solvents, have stifled the progress of realizing practical solution-deposition methods. As a result, organic thin-films used in industry are typically produced by thermal evaporation techniques, which largely negate the benefits due to the higher cost and complexity of vacuum and evaporation equipment. Here we report the use of a conventional office laser printer to electrophotographically deposit the organic semiconductor layer in thin-film transistors. We have successfully used this solvent-free, low-cost method to produce the first laser-printed organic semiconductor layer in thin-film transistors. We printed on flexible and transparent polyethylene terephthalate (PET) substrates. We used the highly hydrophobic fluoropolymer Cytop as the dielectric in a bottom-gate, bottom-contact configuration, a feat that is not possible with traditional solution-deposition. The organic semiconductor layer consisted of a toner powder based on triisopropylsilylethynyl pentacene (TIPS Pn). Grazing incidence wide-angle X-ray scattering (GIWAXS) images indicated both edge- and face-on orientations of the semiconductor for these devices while electrical measurements revealed field-effect mobilities up to 10-3 cm2V¬-1s-1 and on/off current ratio of 103.
Our method has the combined advantages of low temperature and ambient pressure deposition while eliminating the drawbacks of solvents or the high cost of evaporation equipment. Further, as a digital printing method, the laser-printed layer is easily patternable as designed by any convenient graphics software. Since the powder is transferred in a dry state, surface dewetting is no longer an issue, which opens the door to even more substrate/dielectric materials that would otherwise reject solutions from adhering.
The understanding of the nucleation stage of thin film growth is a key element of the optimization of synthesis parameters in order to obtain high-quality optical coatings with predetermined characteristics. The fabrication of advanced coatings, often consisting of complex non-quarter wave and/or metal dielectric stacks, requires new and more powerful in situ monitoring techniques compared to conventional reflectometry and transmission, or quartz crystal microbalance measurements. We describe the use of in situ real-time spectroscopic ellipsometry (RTSE) for the development of optical materials and for the control of the fabrication of homogeneous and inhomogeneous optical filters. Examples include materials such as Ti02, Si02 and SiNx prepared by plasma-enhanced chemical vapor deposition (PECVD).
The present work details a facile and low-temperature (125C) solution-processed Al-doped ZnO (AZO) buffer layer functioning very effectively as electron accepting/hole blocking layer for a wide range of polymer:fullerene bulk heterojunction systems, and yielding power conversion efficiency in excess of 10% (8%) on glass (plastic) substrates. We show that ammonia addition to the aqueous AZO nanoparticle solution is a critically important step toward producing compact and smooth thin films which partially retain the aluminum doping and crystalline order of the starting AZO nanocrystals. The ammonia treatment appears to reduce the native defects via nitrogen incorporation, making the AZO film a very good electron transporter and energetically matched with the fullerene acceptor. Importantly, highly efficient solar cells are achieved without the need for additional surface chemical passivation or modification, which has become an increasingly common route to improving the performance of evaporated or solution-processed ZnO ETLs in solar cells.
The high optical transmittance, electrical conductivity, flexibility and chemical stability of graphene have triggered great interest in its application as a transparent conducting electrode material and as a potential replacement for indium doped tin oxide. However, currently available large scale production methods such as chemical vapor deposition produce polycrystalline graphene, and require additional transfer process which further introduces defects and impurities resulting in a significant increase in its sheet resistance. Doping of graphene with foreign atoms has been a popular route for reducing its sheet resistance which typically comes at a significant loss in optical transmission.
Herein, we report the successful bromine doping of graphene resulting in air-stable transparent conducting electrodes with up to 80% reduction of sheet resistance reaching ~180 Ω/ at the cost of 2-3% loss of optical transmission in case of few layer graphene and 0.8% in case of single layer graphene. The remarkably low tradeoff in optical transparency leads to the highest enhancements in figure of merit reported thus far. Furthermore, our results show a controlled increase in the workfunction up to 0.3 eV with the bromine content. These results should help pave the way for further development of graphene as potentially a highly transparent substitute to other transparent conducting electrodes in optoelectronic devices.
Molecular orientation plays a significant role in determining the performance of small molecule solar cells. Key photovoltaic processes in these cells are strongly dependent on how the molecules are oriented in the active layer. We isolate contributions arising from the bulk molecular orientations vs. those from interfacial orientations in ZnPc/C60 bilayer systems and we probe these contributions by comparing device pairs in which only the bulk or the interface differ. By controlling the orientation in the bulk the current can be strongly modulated, whereas controlling the interfacial molecular orientation and degree of intermixing mediate the voltage.
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