Search

We report on the fabrication of transparent, conductive, mechanically robust electrode composites of poly(triarylamine) (PTAA) doped with different concentrations of carbon nanotubes (CNTs) or graphene nanoplatelets (GNPs). Additionally, the effects of nanofiller surface modification with amines were characterized by comparing the transparency, conductivity, and mechanical properties to composites with unmodified nanofillers. The optimization of the concentrations and fabrication parameters resulted in films with high transparency, improved electrical conductivity, and superior mechanical properties. Amine-functionalized nanofillers more readily dispersed into the matrix, and the addition of 1 wt% amine-CNTs resulted in a composite film with a conductivity of 1.1 S cm− 1 and a transparency of 90–95% in the visible spectrum at a sub-100 nm thickness. At low doping concentrations, composites with amine-functionalized nanofillers exhibited a 100% increase in fracture energy compared to composites with unmodified nanofillers, an effect attributed to increased plasticity of the doped polymer. These findings have applications in many electronic devices that utilize organic semiconducting layers, such as organic light emitting diodes and perovskite photovoltaics.

Organic solar cells subjected to environmental stressors such as heat, moisture, and UV radiation can undergo significant mechanical degradation, leading to delamination of layers and device failure. This paper reports the effect these stressors have on the mechanical integrity of active layers and interfaces as measured by subcritical debonding tests, and the in situ evolution of defects and fracture processes is characterized. At elevated temperatures below 50 °C in inert conditions, significant device weakening was observed, an effect we attributed to a temperature-induced P3HT:PCBM delamination mechanism from the underlying ZnO. At 50 °C in ambient conditions with UV exposure—selected to better simulate real-world environments—devices were more resistant to fracture because of an interfacial strengthening effect from increased hydrogen bonding where UV-induced Zn(OH) 2 formation reinforced the interface with P3HT:PCBM. This photoinduced hydroxylation mechanism was determined from a decrease in the Zn/O ratio with increased UVA or UVB exposure, and hydroxylation was shown to directly correlate with the resistance to fracture in devices.

This paper describes a large increase in the stretchability–i.e., resistance to cracking under tensile deformation–of organic semiconductor films produced by encapsulation. Specifically, encapsulation is shown to greatly suppress crack formation and growth in films of materials relevant to organic solar cells. Encapsulated films of the organic bulk heterojunction blend of poly(3-heptylthiophene) and phenyl-C61-butyric acid methyl ester (P3HpT:PCBM) exhibit greater crack-onset strain, lower crack density, and lower average crack length than unencapsulated films. Films of P3HpT:PCBM on polyurethane (PU) showed cracks at 6.6 ± 0.5% without encapsulation and 40 ± 4% with encapsulation. Films of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) also demonstrate suppressed cracking when encapsulated, as well as reduced dependence of resistance on strain after the crack-onset strain (which indicates a greater usable range of strain for encapsulated vs. unencapsulated films). A finite element model is used to explain the mechanism suppressing crack growth, which involves delocalization of strain around minor defects in the films by the encapsulating substrate. In addition, encapsulation is used to enable the first encapsulated solar cell in which every component is intrinsically stretchable. These cells are stretchable to 9–10% strain, with some cells performing well even after their crack-onset strain of 8–9%, whereas unencapsulated cells fail at 4% strain. This work highlights the necessity to consider encapsulation–already important for protecting the electronically active components of a device from abrasion, weathering, or chemical damage–as an important factor in the mechanical robustness of stretchable devices.

Organic electronic materials have many characteristics that make them attractive for applications in which mechanical deformability—i.e., flexibility and stretchability—are required. While deformation often degrades the performance of these devices, very little is known about the effects of cyclic loading—i.e., mechanical fatigue—on the microstructure and mechanical properties of the active materials. This paper examines the evolution of microstructure, stiffness, and ductility of thin films of poly(3-heptylthiophene) (P3HpT) as the film undergoes cyclic straining using ultraviolet-visible (UV–vis) spectroscopy and film-on-elastomer techniques. Thin films of P3HpT are cyclically stretched by 5, 10, or 25 percent (i.e., below, at, and above the yield point—the point at which the polymer plastically deforms with strain) up to 10000 cycles. UV–vis absorption spectroscopy is taken in intervals and the weakly interacting H-aggregate model is used to determine the aggregate quantity (from the vibronic progression) and quality (from the exciton bandwidth) in the films. Films cyclically strained at 5 and 10 percent (below and at the yield point) do not undergo significant reduction in the aggregated fraction of polymer chains, while films strained to 25% (above the yield point) undergo a reduction in aggregated fraction of over 10% by the 2000th cycle. At 25% strain, a significant reduction in the buckling wavelength from 3.4 ± 0.4 μm to 2.4 ± 0.3 μm is observed within the first 100 strain cycles suggesting a significant reduction in the stiffness and resilience of the films. A significant decrease in ductility is observed in films cyclically strained, and the effect is found to increase with increasing levels of strain. These results suggest that materials cyclically strained below their yield point will retain a microstructure that is their most electronically favorable, and that the mechanical properties of materials strained above their yield point will evolve significantly under repeated deformation. This information can be used to inform design where accommodation of repetitive strain is required, such as outdoor, portable, and wearable devices.

Unlike existing silicon, CIGS, and multi-junction cells that exhibit remarkable mechanical durability, perovskite solar cells have been shown to delaminate when subjected to the mechanical loads that occur during processing and field exposures, limiting their potential as a reliable solar technology. Mechanical reinforcement is thus essential for durable and reliable perovskite technologies. A recent strategy to overcome the thermomechanical fragility of perovskite solar cells is to extrinsically shield them by introducing reinforcing scaffolds which partition the cell into many distinct microcells, but improvements in mechanical stability coincide with a reduced device efficiency due to parasitic absorption by the scaffold. We address this reduced efficiency by integrating concentrating immersion-lens arrays (CILAs) into scaffold-reinforced solar cells. These scaffolds are lithographically patterned by a maskless process, in which ultraviolet light is used to pattern the scaffolds through the CILAs, ensuring self-alignment and optical contact with the microcells. This process creates mm-scale scaffold patterns with a line edge roughness of 17.5 ± 4.3 µm and line width roughness of 26.4 ± 8.5 µm. Perovskite devices are deposited into the microcells, and during operation, light is concentrated into the microcells and away from the insulating scaffolds, resulting in mechanically resilient solar cells with efficiencies comparable to planar devices. The devices with the strongest lenses—i.e., lower radius of curvature—recover up to 89 ± 15% of photocurrent and 91 ± 29% power conversion efficiency that would have been otherwise lost to parasitic absorption. Ray-tracing simulations of the CILAs also demonstrate passive tracking of incident light which is critical for optimal power output as the sun moves across the sky during the day. In these simulations, devices with CILAs showed improved passive tracking compared to devices without CILAs out to 60° off-normal. The UV stability of CILAs are experimentally verified through aging tests which show no change in their mechanical integrity after 1000 h of UV exposure. The simplicity of the fabrication process and the efficiency of the resulting scaffolded devices show that a lens-integrated scaffold-reinforced structure is a potential pathway to high-performance, robust, commercially viable perovskite solar cells.

We report on the inclusion of 5-aminovaleric acid (5-AVA)—a bulky, long-chained organic molecule—as an additive to enhance the mechanical integrity of hybrid perovskite films. We studied a range of organic cation additives and found that 5-AVA was the most effective at improving cohesion energy, a key metric of mechanical reliability. MAPbI3 films reinforced with 5-AVA added in 5% concentration increased cohesion energy 12-fold from 0.53 J/m2 to 6.04 J/m2, an effect which is attributed to increased plasticity and crack deflection around grain boundaries of the additive-containing perovskite. The addition of 5-AVA also improves Voc in perovskite solar cells and carrier lifetimes with a minimal decrease in PCE, attributed to passivation reducing defect and trap densities. A Tauc plot analysis of the bandgap shows that 5-AVA increases the band gap of the perovskite, correlating with reduced film stress compared to MAPbI3. As a result, the usage of 5-AVA improves the intrinsic thermomechanical reliability, but this improvement comes at the penalty of slightly reduced device efficiency due to reduced charge extraction from the presence of the bulky, insulating organic additive.

Despite the intrinsic flexibility of organic electronic materials due to their thinness, a deliberate selection of materials on the basis of their mechanical—not just charge-transport—properties is required for applications with mechanically demanding form factors, such as those that exist in the field of wearable electronics. This paper describes a skin-wearable solar cell enabled by the deliberate selection or intentional plasticization of the components to enable an extreme level of stability under cyclic bending deformations. In particular, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films plasticized with 10% fluorosurfactant are used for both the anode and cathode, with the cathode layer further modified with polyethyleneimine (PEI) to lower the work function. Use of poly(3-heptylthiophene) (P3HpT) instead of the far more common poly(3-hexylthiophene) (P3HT) as the electron donor permitted extreme deformation because of its increased mechanical compliance (owing to its low glass transition temperature). Cells fabricated on 13-µm polyimide tape and adhered to human skin show stable performance when compressively strained by approximately 75%. These compressive strains produce convex and concave buckles with minimum radii of curvature of ca. 100 µm. Finite-element modeling predicts that the films require the ability to withstand a range of strains of 10%, when both convex and concave bends are considered. These devices, enabled by the stretchable semiconductor P3HpT, withstand up to one thousand cycles of compression with less than 20% degradation in power conversion efficiency, whereas devices based on P3HT show greater degradation after only five cycles, and fail catastrophically by fifty cycles. The usefulness of the wearable solar cells is demonstrated by their abilities to power an LED and a digital watch.

Mechanical compliance is a critical attribute for organic semiconductors in flexible, stretchable, mechanically robust, and biologically integrated electronics. This paper substantially develops the observation that a small change in the length of the alkyl side chain of regioregular poly(3-alkylthiophene)s has a dramatic effect on the interplay between their mechanical and charge-transport properties. Specifically, the thermal, mechanical, and charge-transport properties of poly(3-heptylthiophene) (P3HpT, n = 7), which we found to be an unusual example of a stretchable semiconducting thermoplastic, are described in comparison to those of poly(3-hexylthiophene) (P3HT, n = 6) and poly(3-octylthiophene) (P3OT, n = 8). Neat P3HpT was found to have mechanical properties similar to that of P3OT, and when mixed in 1:1 blends with the fullerene [6,6]-phenyl C 61 butyric acid methyl ester (PCBM), exhibited electronic properties comparable to P3HT. However, the charge-carrier mobility of neat P3HpT is substantially inferior to that of P3HT; the good performance of P3HpT-based solar cells is the result of improved mobility in P3HpT:PCBM blends compared to the neat material. While P3HpT may be a favorable alternative to P3HT in ultra-flexible, stretchable, and mechanically robust organic solar cells, P3HpT would only make a good field-effect transistor in situations in which mechanical compliance was more important than high mobility.

Bulk heterojunction films, which typically comprise a polymer donor and fullerene acceptor, are considerably stiffer than films of the neat polymer. The increase in stiffness upon blending is dependent on the miscibility of the polymer and the fullerene, and potentially on the details of molecular mixing, in particular, intercalation of the fullerene molecules between the polymer side chains. This paper describes the effects of molecular mixing on the tensile modulus of polythiophenes in 1:1 blends with [6,6]-phenyl C61 butyric acid methyl ester (PC61BM). A series of four polymers and their blends with PC61BM are tested using mechanical, spectroscopic, and photovoltaic device-based measurements to determine if it is possible to predict trends in the tensile modulus based on the extent of molecular mixing. The four polymers are poly-2,2′:5′,2″-(3,3″-dihexyl-terthiophene) (PT2T), which forms an amorphous, molecularly mixed composite, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), which forms a well ordered blend with bimolecular crystallization, and regioregular poly(3-hexylthiophene) (P3HT) and poly(3-heptylthiophene) (P3HpT), which form a ternary blend with an amorphous mixed phase. The tensile moduli are measured by the buckling technique and correlations are found between the modulus of the neat polymer and the blends. Although spectroscopic and photovoltaic device-based measurements of P3HT:PC61BM and PT2T:PC61BM, along with literature precedent, suggest completely different extents of molecular mixing, they were found to have similar moduli (2.75±0.59 GPa and 2.61±0.39 GPa, after annealing). A strong correlation between the moduli of the blended films and the moduli of the neat polymers suggest that the stiffness of the blend is determined to a large extent by that of the polymer, and is unexpectedly insensitive to the details of molecular mixing, at least for the materials investigated.