Strong Plasmon–Exciton Coupling in Ag Nanoparticle—Conjugated Polymer Core-Shell Hybrid Nanostructures

Strong plasmon-exciton coupling between tightly-bound excitons in organic molecular semiconductors and surface plasmons in metal nanostructures has been studied extensively for a number of technical applications, including low-threshold lasing and room-temperature Bose-Einstein condensates. Typically, excitons with narrow resonances, such as J-aggregates, are employed to achieve strong plasmon-exciton coupling. However, J-aggregates have limited applications for optoelectronic devices compared with organic conjugated polymers. Here, using numerical and analytical calculations, we demonstrate that strong plasmon-exciton coupling can be achieved for Ag-conjugated polymer core-shell nanostructures, despite the broad spectral linewidth of conjugated polymers. We show that strong plasmon-exciton coupling can be achieved through the use of thick shells, large oscillator strengths, and multiple vibronic resonances characteristic of typical conjugated polymers, and that Rabi splitting energies of over 1000 meV can be obtained using realistic material dispersive relative permittivity parameters. The results presented herein give insight into the mechanisms of plasmon-exciton coupling when broadband excitonic materials featuring strong vibrational-electronic coupling are employed and are relevant to organic optoelectronic devices and hybrid metal-organic photonic nanostructures

Charge transfer dynamics in conjugated polymer/MoS2 organic/2D heterojunctions

Heterojunctions between organic and two-dimensional (2D) semiconductors show promising applications in ultrathin electronic and optoelectronic devices, including field-effect transistors, light-emitting diodes, and photovoltaics. These organic/2D heterojunctions form ideal interfaces due to the lack of dangling bonds at the surfaces of the neat (i.e., individual) materials and their propensity to interact via van der Waals forces. Despite this, organic/2D heterojunction devices have had relatively low quantum efficiencies, suggesting limitations on the charge transport within these devices. Understanding the charge transfer dynamics across organic/2D semiconductor interfaces at fundamental time scales is an important part of overcoming these limitations. In this work, we investigate the photoexcited charge carrier dynamics in organic/2D heterojunctions comprised of large-area monolayer MoS2 and solution-deposited organic semiconducting conjugated polymer thin-films. Using photoluminescence and femtosecond transient absorption spectroscopy, we compare the efficiencies of charge transfer for three different conjugated polymer/MoS2 heterojunctions: P3HT, PCDTBT, and PTB7. We show that electron transfer occurs from MoS2 to P3HT in under 9 ps, and from MoS2 to PCDTBT or PTB7 in under 120 fs. Despite this, we demonstrate that the P3HT/MoS2 heterojunction is the most efficient because the transferred charges have an order-of-magnitude increase in their lifetimes, giving rise to enhanced photoluminescence. This work will help guide designs of future organic/2D heterojunctions using scalable fabrication technologies

Organic solar cells: study of combined effects of active layer nanostructure and electron and hole transport layers

An organic solar cell based on Poly (3-hexathiophine-2,5-diyl) and [6,6]-Phenyl C61 butyric acid methyl ester has been subjected to all layers treatment and was investigated for combined effects of the these layers on device performance. These treatment included optimization of active layer morphology and thickness and improving the structure of the hole and electron transport layers, as well as subjecting the full device to optimum post deposition thermal treatment. Such a device has shown an increase in the optical absorption intensity in the near infrared region compared to the reference device, which is thought to be advantageous for producing high current density. The increase in the current density has also been correlated with light trapping within the active layer and the possibility of the occurrence of total internal reflection, which was explained using total internal reflection spectroscopic ellipsometry measurements. The current density-voltage characteristics have been measured in dark and under illumination. Power conversion efficiency as high as 7% has been achieved correlated with a fill factor of 71%

Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites.

Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices1,2. This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively3) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects4. Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance5, perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance6. The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions7 and with local strain8, both of which make devices less stable9. Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process10,11, we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices

Charge Transfer and Enhanced Absorption in MoS2 - Organic Heterojunctions Using Plasmonic Metasurfaces

International audienc

Dominating Interlayer Resonant Energy Transfer in Type-II 2D Heterostructure

Type-II heterostructures (HSs) are essential components of modern electronic and optoelectronic devices. Earlier studies have found that in type-II transition metal dichalcogenide (TMD) HSs, the dominating carrier relaxation pathway is the interlayer charge transfer (CT) mechanism. Here, this report shows that, in a type-II HS formed between monolayers of MoSe2 and ReS2, nonradiative energy transfer (ET) from higher to lower work function material (ReS2 to MoSe2) dominates over the traditional CT process with and without a charge-blocking interlayer. Without a charge-blocking interlayer, the HS area shows 3.6 times MoSe2 photoluminescence (PL) enhancement as compared to the MoSe2 area alone. In a completely encapsulated sample, the HS PL emission further increases by a factor of 6.4. After completely blocking the CT process, more than 1 order of magnitude higher MoSe2 PL emission was achieved from the HS area. This work reveals that the nature of this ET is truly a resonant effect by showing that in a similar type-II HS formed by ReS2 and WSe2, CT dominates over ET, resulting in a severely quenched WSe2 PL. This study not only provides significant insight into the competing interlayer processes but also shows an innovative way to increase the PL emission intensity of the desired TMD material using the ET process by carefully choosing the right material combination for HS