Hanlin Hu

Hybrid Perovskite Thin‐Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

Entanglements in marginal solutions: a means of tuning pre-aggregation of conjugated polymers with positive implications for charge transport

The solution-processing of conjugated polymers, just like commodity polymers, is subject to solvent and molecular weight-dependent solubility, interactions and chain entanglements within the polymer, all of which can influence the crystallization and microstructure development in semi-crystalline polymers and consequently affect charge transport and optoelectronic properties. Disentanglement of polymer chains in marginal solvents was reported to work via ultrasonication, facilitating the formation of photophysically ordered polymer aggregates. In this contribution, we explore how a wide range of technologically relevant solvents and formulations commonly used in organic electronics influence chain entanglement and the aggregation behaviour of P3HT using a combination of rheological and spectrophotometric measurements. The specific viscosity of the solution offers an excellent indication of the degree of entanglements in the solution, which is found to be related to the solubility of P3HT in a given solvent. Moreover, deliberately disentangling the solution in the presence of solvophobic driving forces, leads consistently to formation of photophysically visible aggregates which is indicative of local and perhaps long range order in the solute. We show for a broad range of solvents and molecular weights that disentanglement ultimately leads to significant ordering of the polymer in the solid state and a commensurate increase in charge transport properties. In doing so we demonstrate a remarkable ability to tune the microstructure which has important implications for transport properties. We discuss its potential implications in the context of organic electronics and photovoltaics.

Stable High‐Performance Perovskite Solar Cells via Grain Boundary Passivation

The trap states at grain boundaries (GBs) within polycrystalline perovskite films deteriorate their optoelectronic properties, making GB engineering particularly important for stable high-performance optoelectronic devices. It is demonstrated that trap states within bulk films can be effectively passivated by semiconducting molecules with Lewis acid or base functional groups. The perovskite crystallization kinetics are studied using in situ synchrotron-based grazing-incidence X-ray scattering to explore the film formation mechanism. A model of the passivation mechanism is proposed to understand how the molecules simultaneously passivate the Pb-I antisite defects and vacancies created by under-coordinated Pb atoms. In addition, it also explains how the energy offset between the semiconducting molecules and the perovskite influences trap states and intergrain carrier transport. The superior optoelectronic properties are attained by optimizing the molecular passivation treatments. These benefits are translated into significant enhancements of the power conversion efficiencies to 19.3%, as well as improved environmental and thermal stability of solar cells. The passivated devices without encapsulation degrade only by ≈13% after 40 d of exposure in 50% relative humidity at room temperature, and only ≈10% after 24 h at 80 °C in controlled environment.

Highly efficient polymer solar cells with printed photoactive layer: rational process transfer from spin-coating

Scalable and continuous roll-to-roll manufacturing is at the heart of the promise of low-cost and high throughput manufacturing of solution-processed photovoltaics. Yet, to date the vast majority of champion organic solar cells reported in the literature rely on spin-coating of the photoactive bulk heterojunction (BHJ) layer, with the performance of printed solar cells lagging behind in most instances. Here, we investigate the performance gap between polymer solar cells prepared by spin-coating and blade-coating the BHJ layer for the important class of modern polymers exhibiting no long range crystalline order. We find that thickness parity does not always yield performance parity even when using identical formulations. Significant differences in the drying kinetics between the processes are found to be responsible for BHJ nanomorphology differences. We propose an approach which benchmarks the film drying kinetics and associated BHJ nanomorphology development against those of the champion laboratory devices prepared by spin-coating the BHJ layer by adjusting the process temperature. If the optimization requires the solution concentration to be changed, then it is crucial to maintain the additive-to-solute volume ratio. Emulating the drying kinetics of spin-coating is also shown to help achieve morphological and performance parities. We put this approach to the test and demonstrate printed PTB7:PC71BM polymer solar cells with efficiency of 9% and 6.5% PCEs on glass and flexible PET substrates, respectively. We further demonstrate performance parity for two other popular donor polymer systems exhibiting rigid backbones and absence of a long range crystalline order, achieving a PCE of 9.7%, the highest efficiency reported to date for a blade coated organic solar cell. The rational process transfer illustrated in this study should help the broader and successful adoption of scalable printing methods for these material systems.

Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates

We demonstrate that local and long-range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

Ultra-low p-doping of poly(3-hexylthiophene) and its impact on polymer aggregation and photovoltaic performance

Abstract Poly(3-hexylthiophene) (P3HT) films and P3HT / fullerene photovoltaic cells have been p-doped with very low levels (< 1 wt. %) of molybdenum tris[1-(trifluoromethylcarbonyl)- 2-(trifluoromethyl)-ethane-1,2-dithiolene]. The dopants are inhomogenously distributed within doped P3HT films, both laterally and as a function of depth, and appear to aggregate in some instances. Doping also results in subtle changes in the local and long range order of the P3HT film. These effects likely contribute to the complexity of the observed evolutions in conductivity, mobility and work function with doping levels. They also negatively affect the open-circuit voltage and fill factor of solar cells in unexpected ways, indicating that dopant aggregation and non-uniform distribution can harm device performance.

Nanoscale energetic mapping of bulk heterojunction solar cells (Conference Presentation)

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.

Hybrid tandem quantum dot/organic photovoltaic cells with complementary near infrared absorption

Monolithically integrated hybrid tandem solar cells that effectively combine solution-processed colloidal quantum dot (CQD) and organic bulk heterojunction subcells to achieve tandem performance that surpasses the individual subcell efficiencies have not been demonstrated to date. In this work, we demonstrate hybrid tandem cells with a low bandgap PbS CQD subcell harvesting the visible and near-infrared photons and a polymer:fullerene-poly (diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C60-butyric acid methyl ester (PC61BM)-top cell absorbing effectively the red and near-infrared photons of the solar spectrum in a complementary fashion. The two subcells are connected in series via an interconnecting layer (ICL) composed of a metal oxide layer, a conjugated polyelectrolyte, and an ultrathin layer of Au. The ultrathin layer of Au forms nano-islands in the ICL, reducing the series resistance, increasing the shunt resistance, and enhancing the device fill-factor. The hybrid tandems reach a power conversion efficiency (PCE) of 7.9%, significantly higher than the PCE of the corresponding individual single cells, representing one of the highest efficiencies reported to date for hybrid tandem solar cells based on CQD and polymer subcells.