Charge Transport Modulation of a Flexible Quantum Dot Solar Cell Using a Piezoelectric Effect

© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Colloidal quantum dots are promising materials for flexible solar cells, as they have a large absorption coefficient at visible and infrared wavelengths, a band gap that can be tuned across the solar spectrum, and compatibility with solution processing. However, the performance of flexible solar cells can be degraded by the loss of charge carriers due to recombination pathways that exist at a junction interface as well as the strained interface of the semiconducting layers. The modulation of the charge carrier transport by the piezoelectric effect is an effective way of resolving and improving the inherent material and structural defects. By inserting a porous piezoelectric poly(vinylidenefluoride-trifluoroethylene) layer so as to generate a converging electric field, it is possible to modulate the junction properties and consequently enhance the charge carrier behavior at the junction. This study shows that due to a reduction in the recombination and an improvement in the carrier extraction, a 38% increase in the current density along with a concomitant increase of 37% in the power conversion efficiency of flexible quantum dots solar cells can be achieved by modulating the junction properties using the piezoelectric effect

Polymer network hole transport layers based on photochemically cross-linkable N′N′-diallyl amide tri-N-substituted triazatruxene monomers

Novel phtotpolymerisable hole-transport layers based on novel triazatruxenes incorporating six non-conjugated dienes as photo cross-linkable end-groups attached to flexible, aliphatic spacers have been synthesised using simple one-step substitution reactions. Hole-only test devices, fabricated using a combination of solution-deposition, spin-coating and initiator-free photochemical cross-linking of these photopolymerisable triazatruxenes, exhibit almost identical current density vs. voltage profiles before and after cross-linking, and as such, represent a promising new class of hole-transport layer for plastic electronic devices

Mechanical Properties of a Library of Low-Band-Gap Polymers

The mechanical properties of low-band-gap polymers are important for the long-term survivability of roll-to-roll processed organic electronic devices. Such devices, e.g., solar cells, displays, and thin-film transistors, must survive the rigors of roll-to-roll coating and also thermal and mechanical forces in the outdoor environment and in stretchable and ultraflexible form factors. This paper measures the stiffness (tensile modulus), ductility (crack-onset strain), or both of a combinatorial library of 51 low-band-gap polymers. The purpose of this study is to systematically screen a library of low-band-gap polymers to better understand the connection between molecular structures and mechanical properties in order to design conjugated polymers that permit mechanical robustness and even extreme deformability. While one of the principal conclusions of these experiments is that the structure of an isolated molecule only partially determines the mechanical propertiesanother important codeterminant is the packing structuresome general trends can be identified. (1) Fused rings tend to increase the modulus and decrease the ductility. (2) Branched side chains have the opposite effect. Despite the rigidity of the molecular structure, the most deformable films can be surprisingly compliant (modulus ≥ 150 MPa) and ductile (crack-onset strain ≤ 68%). This paper concludes by proposing a new composite merit factor that combines the power conversion efficiency in a fully solution processed device obtained via roll and roll-to-roll coating and printing (as measured in an earlier paper) and the mechanical deformability toward the goal of producing modules that are both efficient and mechanically stable

Inducing Elasticity through Oligo-Siloxane Crosslinks for Intrinsically Stretchable Semiconducting Polymers

The promise of wearable and implantable devices has made stretchable organic semiconductors highly desirable. Though there are increasing attempts to design intrinsically stretchable conjugated polymers, their performance in terms of charge carrier mobility and maximum fracture strain is still lacking behind extrinsic approaches (i.e., buckling, Kirigami interconnects). Here, polymer crosslinking with flexible oligomers is applied as a strategy to reduce the tensile modulus and improve fracture strain, as well as fatigue resistance for a high mobility diketopyrrolopyrrole polymer. These polymers are crosslinked with siloxane oligomers to give stretchable films stable up to a strain ε = 150% and 500 strain‐and‐release cycles of 100% strain without the formation of nanocracks. Organic field‐effect transistors are prepared to assess the electrical properties of the crosslinked film under cyclic strain loading. An initial average mobility (μavg) of 0.66 cm2 V−1 s−1 is measured at 0% strain. A steady μavg above 0.40 cm2 V−1 s−1 is obtained in the direction perpendicular to the strain direction after 500 strain‐and‐release cycles of 20% strain. The μavg in the direction parallel to strain, however, is compromised due to the formation of wrinkles

An Efficient, “Burn in” Free Organic Solar Cell Employing a Nonfullerene Electron Acceptor

A comparison of the efficiency, stability, and photophysics of organic solar cells employing poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′″-di(2-octyldodecyl)-2,2′;5′,2″;5″,2′″-quaterthiophen-5,5′″-diyl)] (PffBT4T-2OD) as a donor polymer blended with either the nonfullerene acceptor EH-IDTBR or the fullerene derivative, [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) as electron acceptors is reported. Inverted PffBT4T-2OD:EH-IDTBR blend solar cell fabricated without any processing additive achieves power conversion efficiencies (PCEs) of 9.5 ± 0.2%. The devices exhibit a high open circuit voltage of 1.08 ± 0.01 V, attributed to the high lowest unoccupied molecular orbital (LUMO) level of EH-IDTBR. Photoluminescence quenching and transient absorption data are employed to elucidate the ultrafast kinetics and efficiencies of charge separation in both blends, with PffBT4T-2OD exciton diffusion kinetics within polymer domains, and geminate recombination losses following exciton separation being identified as key factors determining the efficiency of photocurrent generation. Remarkably, while encapsulated PffBT4T-2OD:PC71BM solar cells show significant efficiency loss under simulated solar irradiation (“burn in” degradation) due to the trap-assisted recombination through increased photoinduced trap states, PffBT4T-2OD:EH-IDTBR solar cell shows negligible burn in efficiency loss. Furthermore, PffBT4T-2OD:EH-IDTBR solar cells are found to be substantially more stable under 85 °C thermal stress than PffBT4T-2OD:PC71BM devices

Stability of Polymer:PCBM Thin Films under Competitive Illumination and Thermal Stress

The combined effects of illumination and thermal annealing on the morphological stability and photodimerization in polymer/fullerene thin films are examined. While illumination is known to cause fullerene dimerization and thermal stress their dedimerization, the operation of solar cells involves exposure to both. The competitive outcome of these factors with blends of phenyl‐C61‐butyric acid methyl ester (PCBM) and polystyrene (PS), supported on PEDOT:PSS is quantified. UV–vis spectroscopy is employed to quantify dimerization, time‐resolved neutron reflectivity to resolve the vertical composition stratification, and atomic force microscopy for demixing and coarsening in thin films. At the conventional thermal stress test temperature of 85 °C (and even up to the PS glass transition), photodimerization dominates, resulting in relative morphological stability. Prior illumination is found to result in improved stability upon high temperature annealing, compatible with the need for dedimerization to occur prior to structural relaxation. Modeling of the PCBM surface segregation data suggests that only PCBM monomers are able to diffuse and that illumination provides an effective means to control dimer population, and thus immobile fullerene fraction, in the timescales probed. The results provide a framework for understanding of the stability of organic solar cells under operating conditions

Semiconducting polymers for stretchable, ultra-flexible, and mechanically robust organic photovoltaics

The original vision of organic electronics comprises the use of organic conductors and semiconductors specifically designed to accommodate large strains to enable highly deformable and mechanically robust devices for organic photovoltaics, biosensors, and electronic skins. However, mechanical properties of organic materials are often overlooked; as a result, many of these materials are unable to accommodate the mechanical stresses required for their intended applications. Thus, it is important to understand the parameters that govern mechanical properties of these materials. Chapter 1 provides an introduction to the characteristics, applications, and fabrications of stretchable electronics. The idea of intrinsically stretchable electronics comprising molecularly designs of semiconducting polymers is outlined. Chapter 2 focuses on the mechanical degradation and stability of organic solar cells. The key highlights are the importance of mechanical properties and mechanical effects on the viability of organic solar cells during manufacture and in operational environment. Chapter 3 and Appendix A investigate the effects of the length of the alkyl side chains in poly(3-alkylthiophenes) on the deformability of the pure polymer films and their blends with fullerenes. Chapter 4, 5, and Appendix B provide studies on the inherent competition between good photovoltaic performance and mechanical compliance; a critical length of the alkyl side chains on the poly(3-alkylthiophene) allows for co-optimization of both photovoltaic and mechanical properties. In Chapter 6 and Appendix C, the effect of incompletely separated grades of electron acceptors on the mechanical deformability of organic solar cells is investigated in an effort to simultaneously improve the mechanical robustness of the organic solar cells and reduce the energy of production. Chapter 7 describes the plasticization of the common transparent electrode using common processing additives. Chapter 8, 9, and 10 investigate the mechanical properties of low-bandgap polymers as the function of the molecular structure and solid-state packing. Chapter 11 introduces a novel experimental method, photovoltaic mapping (PVMAP), which combines the use of non-damaging electrode and gradients in processing parameter to spatially map the photovoltaic properties of organic solar cells

Modification of amphiphilic block copolymers for responsive and biologically active surfactants in complex droplets

Concerns regarding the speed and portability of sensing devices have spurred development of numerous novel platforms. Complex emulsions with responsive surfactants have emerged as a promising class of materials for the detection of various pathogens and environmental toxins. Herein, we report a study of the amphiphilic block copolymer surfactant (BCP), polystyrene-block-poly(acrylic acid), and its use as a functional surfactant. We observe that the composition and molecular weight of BCPs affect the interfacial properties, specifically, more amphiphilic BCPs lead to greater reductions in interfacial tension at the water/oil interface. We further demonstrate that conformational change of poly(acrylic acid) leads to changes in the interfacial tension reductions at these interfaces. Next, we present modification of BCPs with trypsin through carbodiimide mediated amidation to produce functional BCP-trypsin. The modified polymers retain their surfactant capabilities, as well as the functionality of the initial trypsin. Furthermore, we successfully demonstrate the use of the modified polymers within the active complex emulsion framework and the ability of the emulsion framework to turn “on” and “off” functionality through shielding of the active compounds. These responses to chemical changes in their surrounding environment illustrate the potential use of amphiphilic block copolymers as the key component of a complex emulsion systems for sensing device that is rapid, portable, and produces results in real-time. © 2022 The Author(s)Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Morphology-dependent luminescence in complex liquid colloids

Complex liquid colloids hold great promise as transducers in sensing applications as a result of their tunable morphology and intrinsic optical properties. Herein, we introduce meta-amino substituted green fluorescence protein chromophore (GFPc) surfactants that localize at the organic-water interface of complex multiphase liquid colloids. The meta-amino GFPc exhibits hydrogen-bonding (HB) mediated fluorescence quenching, and are nearly nonemissive in the presence of protic solvents. We demonstrate morphology-dependent fluorescence of complex liquid colloids and investigate the interplay between GFPc surfactants and other simple surfactants. This environmentally responsive surfactant allows us to observe morphological changes of complex emulsions in randomized orientations. We demonstrate utility with an enzyme activity based fluorescence "turn-ON" scheme. The latter employs an oligopeptide-linked GFPc that functions as both a surfactant and trypsin target. The cleavage of hydrophilic peptide results in a morphology change and ultimately a fluorescence turn-on. Fluorescent complex colloids represent a new approach for biosensing in liquid environments. Copyright © 2019 American Chemical Society