Spin relaxation of electron and hole polarons in ambipolar conjugated polymers.

The charge-transport properties of conjugated polymers have been studied extensively for opto-electronic device applications. Some polymer semiconductors not only support the ambipolar transport of electrons and holes, but do so with comparable carrier mobilities. This opens the possibility of gaining deeper insight into the charge-transport physics of these complex materials via comparison between electron and hole dynamics while keeping other factors, such as polymer microstructure, equal. Here, we use field-induced electron spin resonance spectroscopy to compare the spin relaxation behavior of electron and hole polarons in three ambipolar conjugated polymers. Our experiments show unique relaxation regimes as a function of temperature for electrons and holes, whereby at lower temperatures electrons relax slower than holes, but at higher temperatures, in the so-called spin-shuttling regime, the trend is reversed. On the basis of theoretical simulations, we attribute this to differences in the delocalization of electron and hole wavefunctions and show that spin relaxation in the spin shuttling regimes provides a sensitive probe of the intimate coupling between charge and structural dynamics.

Room-temperature optically detected magnetic resonance of single defects in hexagonal boron nitride.

Optically addressable solid-state spins are important platforms for quantum technologies, such as repeaters and sensors. Spins in two-dimensional materials offer an advantage, as the reduced dimensionality enables feasible on-chip integration into devices. Here, we report room-temperature optically detected magnetic resonance (ODMR) from single carbon-related defects in hexagonal boron nitride with up to 100 times stronger contrast than the ensemble average. We identify two distinct bunching timescales in the second-order intensity-correlation measurements for ODMR-active defects, but only one for those without an ODMR response. We also observe either positive or negative ODMR signal for each defect. Based on kinematic models, we relate this bipolarity to highly tuneable internal optical rates. Finally, we resolve an ODMR fine structure in the form of an angle-dependent doublet resonance, indicative of weak but finite zero-field splitting. Our results offer a promising route towards realising a room-temperature spin-photon quantum interface in hexagonal boron nitride.

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers.

Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII , without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII . This mixed-valence structure exhibits a 104 -fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d z 2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.

Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds.

We investigate the charge transport physics of a previously unidentified class of electron-deficient conjugated polymers that do not contain any single bonds linking monomer units along the backbone but only double-bond linkages. Such polymers would be expected to behave as rigid rods, but little is known about their actual chain conformations and electronic structure. Here, we present a detailed study of the structural and charge transport properties of a family of four such polymers. By adopting a copolymer design, we achieve high electron mobilities up to 0.5 cm2 V-1 s-1 Field-induced electron spin resonance measurements of charge dynamics provide evidence for relatively slow hopping over, however, long distances. Our work provides important insights into the factors that limit charge transport in this unique class of polymers and allows us to identify molecular design strategies for achieving even higher levels of performance.

Resolving Different Physical Origins toward Crystallite Imperfection in Semiconducting Polymers: Crystallite Size vs Paracrystallinity.

The crystallization and aggregation behaviors of semiconducting polymers play a critical role in determining the ultimate performance of optoelectronic devices based on these materials. Due to the soft nature of polymers, crystallite imperfection exists ubiquitously. To this aspect, crystallinity is often used to represent the degree of crystallite imperfection in a reciprocal relation. Despite of the importance, the discussion on crystallinity is still on the phenomenological level and ambiguous in many cases. As two major contributors to crystallite imperfection, crystallite size and paracrystallinity are highly intertwined and hardly separated, hindering more accurate and trustworthy structural analysis. Herein, with the aid of synchrotron-based X-ray diffraction, combined with environmentally controlled heating capability, the evolution of crystallite size and paracrystallinity of two prototypical polythiophene-based thin films have been successfully measured. Strikingly, the paracrystallinity of poly(3-hexylthiophene-2,5-diyl) (P3HT) crystallites remains unchanged with annealing, while the paracrystallinity of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) becomes diminished with crystallite growth. This work delivers a promising gesture to semiconducting polymers community, confirming that it is possible to experimentally separate crystallite size and paracrystallinity, both of which are highly intertwined. With this progress, investigation on the correlation between further detailed microstructural parameters and device performance can be achieved.

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron-Deficient Polymer Processed by Solution Shear Coating.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V-1 s-1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties.

Chain Coupling and Luminescence in High-Mobility, Low-Disorder Conjugated Polymers.

Optoelectronic devices based on conjugated polymers often rely on multilayer device architectures, as it is difficult to design all the different functional requirements, in particular the need for efficient luminescence and fast carrier transport, into a single polymer. Here we study the photophysics of a recently discovered class of conjugated polymers with high charge carrier mobility and low degree of energetic disorder and investigate whether it is possible in this system to achieve by molecular design a high photoluminescence quantum yield without sacrificing carrier mobility. Tracing exciton dynamics over femtosecond to microsecond time scales, we show that nearly all nonradiative exciton recombination arises from interactions between chromophores on different chains. We evaluate the temperature dependence and role of electron-phonon coupling leading to fast internal conversion in systems with strong interchain coupling and the extent to which this can be turned off by varying side chain substitution. By sterically decreasing interchain interaction, we present an effective approach to increase the fluorescence quantum yield of low-energy gap polymers. We present a red-NIR-emitting amorphous polymer with the highest reported film luminescence quantum efficiency of 18% whose mobility concurrently exceeds that of amorphous-Si. This is a key result toward the development of single-layer optoelectronic devices that require both properties.

Tuning the effective spin-orbit coupling in molecular semiconductors.

The control of spins and spin to charge conversion in organics requires understanding the molecular spin-orbit coupling (SOC), and a means to tune its strength. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. Here we present a systematic study of the g-tensor shift in molecular semiconductors and link it directly to the SOC strength in a series of high-mobility molecular semiconductors with strong potential for future devices. The results demonstrate a rich variability of the molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 to 0.15 µs, for isolated molecules in solution and relate our findings for isolated molecules in solution to the spin relaxation mechanisms that are likely to be relevant in solid state systems.

Charge-Transport Anisotropy in a Uniaxially Aligned Diketopyrrolopyrrole-Based Copolymer.

Aligned films of a semiconducting DPP-based copolymer exhibit highly anisotropic charge transport with a band-like temperature dependence along the alignment direction and hole mobilities of up to 6.7 cm(2) V(-1) s(-1) . X-ray diffraction measurements reveal an exceptional degree of in-plane alignment, high crystallinity, and a dominant face-on orientation of the polymer backbones. The surprising charge-transport properties are interpreted in a tie-chain model consistent with anisotropic activation energies.

Characterization of the angular memory effect of scattered light in biological tissues.

High resolution optical microscopy is essential in neuroscience but suffers from scattering in biological tissues and therefore grants access to superficial brain layers only. Recently developed techniques use scattered photons for imaging by exploiting angular correlations in transmitted light and could potentially increase imaging depths. But those correlations ('angular memory effect') are of a very short range and should theoretically be only present behind and not inside scattering media. From measurements on neural tissues and complementary simulations, we find that strong forward scattering in biological tissues can enhance the memory effect range and thus the possible field-of-view by more than an order of magnitude compared to isotropic scattering for ∼1 mm thick tissue layers.

Enabling high-mobility, ambipolar charge-transport in a DPP-benzotriazole copolymer by side-chain engineering.

In this article we discuss the synthesis of four new low band-gap co-polymers based on the diketopyrrolopyrrole (DPP) and benzotriazole (BTZ) monomer unit. We demonstrate that the BTZ unit allows for additional solubilizing side-chains on the co-monomer and show that the introduction of a linear side-chain on the DPP-unit leads to an increase in thin-film order and charge-carrier mobility if a sufficiently solubilizing, branched, side chain is attached to the BTZ. We compare two different synthetic routes, direct arylation and Suzuki-polycondensation, by a direct comparison of polymers obtained via the two routes and show that direct arylation produces polymers with lower electrical performance which we attribute to a higher density of chain Furthermore we demonstrate that a polymer utilizing this design motif and synthesized via Suzuki-polycondensation ((l-C18)-DPP-(b-C17)-BTZ) exhibits exceptionally high and near balanced average electron and hole mobilities >2 cm2 V-1 s-1 which are among the highest, robustly extracted mobility values reported for DPP copolymers in a top-gate configuration to date. Our results demonstrate clearly that linear side chain substitution of the DPP unit together with co-monomers that allow for the use of sufficiently long or branched solubilizing side chains can be an attractive design motif for solution processable, high mobility DPP copolymers.