Influence of Peptoid Sequence on the Mechanisms and Kinetics of 2D Assembly.

Two-dimensional (2D) materials have attracted intense interest due to their potential for applications in fields ranging from chemical sensing to catalysis, energy storage, and biomedicine. Recently, peptoids, a class of biomimetic sequence-defined polymers, have been found to self-assemble into 2D crystalline sheets that exhibit unusual properties, such as high chemical stability and the ability to self-repair. The structure of a peptoid is close to that of a peptide except that the side chains are appended to the amide nitrogen rather than the α carbon. In this study, we investigated the effect of peptoid sequence on the mechanism and kinetics of 2D assembly on mica surfaces using in situ AFM and time-resolved X-ray scattering. We explored three distinct peptoid sequences that are amphiphilic in nature with hydrophobic and hydrophilic blocks and are known to self-assemble into 2D sheets. The results show that their assembly on mica starts with deposition of aggregates that spread to establish 2D islands, which then grow by attachment of peptoids, either monomers or unresolvable small oligomers, following well-known laws of crystal step advancement. Extraction of the solubility and kinetic coefficient from the dependence of the growth rate on peptoid concentration reveals striking differences between the sequences. The sequence with the slowest growth rate in bulk and with the highest solubility shows almost no detachment; i.e., once a growth unit attaches to the island edge, there is almost no probability of detaching. Furthermore, a peptoid sequence with a hydrophobic tail conjugated to the final carboxyl residue in the hydrophilic block has enhanced hydrophobic interactions and exhibits rapid assembly both in the bulk and on mica. These assembly outcomes suggest that, while the π-π interactions between adjacent hydrophobic blocks play a major role in peptoid assembly, sequence details, particularly the location of charged groups, as well as interaction with the underlying substrate can significantly alter the thermodynamic stability and assembly kinetics.

Composition Dictates Molecular Orientation at the Heterointerfaces of Vapor-Deposited Glasses.

Physical vapor deposition (PVD) can prepare organic glasses with a preferred molecular orientation. The relationships between deposition conditions and orientation have been extensively investigated in the film bulk. The role of interfaces on the structure is less well understood and remains a key knowledge gap, as the interfacial region can govern glass stability and optoelectronic properties. Robust experimental characterization has remained elusive due to complexities in interrogating molecular organization in amorphous, organic materials. Polarized soft X-rays are sensitive to both the composition and the orientation of transition dipole moments in the film, making them uniquely suited to probe molecular orientation in amorphous soft matter. Here, we utilize polarized resonant soft X-ray reflectivity (P-RSoXR) to simultaneously depth profile the composition and molecular orientation of a bilayer prepared through the physical vapor deposition of 1,4-di-[4-(N,N-diphenyl)amino]styryl-benzene (DSA-Ph) on a film of aluminum-tris(8-hydroxyquinoline) (Alq3). The bulk orientation of the DSA-Ph layer is controlled by varying deposition conditions. Utilizing P-RSoXR to depth profile the films enables determination of both the bulk orientation of DSA-Ph and the orientation near the Alq3 interface. At the Alq3 surface, DSA-Ph always lies with its long axis parallel to the interface, before transitioning into the bulk orientation. This is likely due to the lower mobility and higher glass transition of Alq3, as the first several monolayers of DSA-Ph deposited on Alq3 appear to behave as a blend. We further show how orientation at the interface correlates with the bulk behavior of a codeposited glass of similar blend composition, demonstrating a straightforward approach to predicting molecular orientation at heterointerfaces. This work provides key insights into how molecules orient during vapor deposition and offers methods to predict this property, a critical step toward controlling interfacial behavior in soft matter.

Determining Structure and Thermodynamics of A-b-(B-r-C) Copolymers.

The self-assembly of block copolymers (BCPs) is dictated by their segregation strength, χN, and while there are well-developed methods for determining χ in the weak and strong segregation regimes, it is challenging to accurately measure χ of copolymers with intermediate segregation strengths, especially when copolymers have inaccessible order-disorder transition temperatures. χeff is often approximated by using strong segregation theory (SST), but utilizing these values to estimate the interface width (wm) of BCPs in the intermediate segregation regime often results in predictions that deviate significantly from measured values. Therefore, we propose using the extent of mixing, quantified as the normalized interface width wm/L0, where L0 is the block copolymer pitch, as a thermodynamic parameter. We experimentally measure wm and L0 for a series of lamellar A-b-(B-r-C) copolymers via resonant soft X-ray reflectivity and extract values of χeffN based on previous data collected for A-b-B copolymers. The composition profiles measured via reflectivity match the extracted χeffN values, while those calculated with SST predict much more mixed composition profiles. The extracted χeff values agreed quantitatively between copolymers of different molecular weights. We believe that this methodology will be well-suited for block copolymers used in lithographic applications due to their inaccessible order-disorder transition temperatures, intermediate values of χN, and the importance of wm for line edge roughness metrics.

High Sensitivity of Non-Fullerene Organic Solar Cells Morphology and Performance to a Processing Additive.

Although solvent additives are used to optimize device performance in many novel non-fullerene acceptor (NFA) organic solar cells (OSCs), the effect of processing additives on OSC structures and functionalities can be difficult to predict. Here, two polymer-NFA OSCs with highly sensitive device performance and morphology to the most prevalent solvent additive chloronaphthalene (CN) are presented. Devices with 1% CN additive are found to nearly double device efficiencies to 10%. However, additive concentrations even slightly above optimum significantly hinder device performance due to formation of undesirable morphologies. A comprehensive analysis of device nanostructure shows that CN is critical to increasing crystallinity and optimizing phase separation up to the optimal concentration for suppressing charge recombination and maximizing performance. Here, domain purity and crystallinity are highly correlated with photocurrent and fill factors. However, this effect is in competition with uncontrolled crystallization of NFAs that occur at CN concentrations slightly above optimal. This study highlights how slight variations of solvent additives can impart detrimental effects to morphology and device performance of NFA OSCs. Therefore, successful scale-up processing of NFA-based OSCs will require extreme formulation control, a tuned NFA structure that resists runaway crystallization, or alternative methods such as additive-free fabrication.

Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor.

The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution. To overcome these challenges, we use polarized resonant soft X-ray reflectivity (p-RSoXR) to measure nanometer-resolved, molecular orientation depth profiles of vapor-deposited thin films of an organic semiconductor Tris(4-carbazoyl-9-ylphenyl)amine (TCTA). Our depth profiling approach characterizes the vertical distribution of molecular orientation and reveals that molecules near the inorganic substrate and free surface have a different, nearly isotropic orientation compared to those of the anisotropic bulk. Comparison of p-RSoXR results with near-edge X-ray absorption fine structure spectroscopy and optical spectroscopies reveals that TCTA molecules away from the interfaces are predominantly planar, which may contribute to their attractive charge transport qualities. Buried interfaces are further investigated in a TCTA bilayer (each layer deposited under separate conditions resulting in different orientations) in which we find a narrow interface between orientationally distinct layers extending across ≈1 nm. Coupling this result with molecular dynamics simulations provides additional insight into the formation of interfacial structure. This study characterizes the local molecular orientation at various types of buried interfaces in vapor-deposited glasses and provides a foundation for future studies to develop critical structure-function relationships.

Evidence That Sharp Interfaces Suppress Recombination in Thick Organic Solar Cells.

Commercialization and scale-up of organic solar cells (OSCs) using industrial solution printing require maintaining maximum performance at active-layer thicknesses >400 nm─a characteristic still not generally achieved in non-fullerene acceptor OSCs. NT812/PC71BM is a rare system, whose performance increases up to these thicknesses due to highly suppressed charge recombination relative to the classic Langevin model. The suppression in this system, however, uniquely depends on device processing, pointing toward the role of nanomorphology. We investigate the morphological origins of this suppressed recombination by combining results from a suite of X-ray techniques. We are surprised to find that while all investigated devices are composed of pure, similarly aggregated nanodomains, Langevin reduction factors can still be tuned from ∼2 to >1000. This indicates that pure aggregated phases are insufficient for non-Langevin (reduced) recombination. Instead, we find that large well-ordered conduits and, in particular, sharp interfaces between domains appear to help to keep opposite charges separated and percolation pathways clear for enhanced charge collection in thick active layers. To our knowledge, this is the first quantitative study to isolate the donor/acceptor interfacial width correlated with non-Langevin charge recombination. This new structure-property relationship will be key to successful commercialization of printed OSCs at scale.

Label-free characterization of organic nanocarriers reveals persistent single molecule cores for hydrocarbon sequestration.

Self-assembled molecular nanostructures embody an enormous potential for new technologies, therapeutics, and understanding of molecular biofunctions. Their structure and function are dependent on local environments, necessitating in-situ/operando investigations for the biggest leaps in discovery and design. However, the most advanced of such investigations involve laborious labeling methods that can disrupt behavior or are not fast enough to capture stimuli-responsive phenomena. We utilize X-rays resonant with molecular bonds to demonstrate an in-situ nanoprobe that eliminates the need for labels and enables data collection times within seconds. Our analytical spectral model quantifies the structure, molecular composition, and dynamics of a copolymer micelle drug delivery platform using resonant soft X-rays. We additionally apply this technique to a hydrocarbon sequestrating polysoap micelle and discover that the critical organic-capturing domain does not coalesce upon aggregation but retains distinct single-molecule cores. This characteristic promotes its efficiency of hydrocarbon sequestration for applications like oil spill remediation and drug delivery. Such a technique enables operando, chemically sensitive investigations of any aqueous molecular nanostructure, label-free.

Evidence for Field-Dependent Charge Separation Caused by Mixed Phases in Polymer-Fullerene Organic Solar Cells.

As organic photovoltaic performance approaches 20% efficiencies, causal structure-performance relationships must be established for devices to realize theoretical limits and become commercially competitive. Here, we reveal evidence of a causal relationship between mixed donor-acceptor interfaces and charge generation in polymer-fullerene solar cells. To do this, we combine a holistic loss analysis of device performance with quantitative synchrotron X-ray nanocharacterization to identify a >98% anticorrelation between field-dependent geminate recombination and nanodomain purity. Importantly, our analysis eliminates other possible explanations of the performance trends, a requirement to establish causality. The unprecedented granular level of our analysis also separates field-dependent and field-independent recombination at the interface, where we find for the first time that this system is free of field-independent recombination, a loss channel that plagues high-performance systems, including those with non-fullerene acceptors. This result broadens the case that minimizing mixed phases to promote sharp interfaces between pure aggregated domains is the ideal nanostructure for realizing theoretical efficiency limits of organic photovoltaics.

Absolute intensity calibration for carbon-edge soft X-ray scattering.

Resonant soft X-ray scattering (RSOXS) has become a premier probe to study complex three-dimensional nanostructures in soft matter through combining the robust structural characterization of small-angle scattering with the chemical sensitivity of spectroscopy. This technique borrows many of its analysis methods from alternative small-angle scattering measurements that utilize contrast variation, but thus far RSOXS has been unable to reliably achieve an absolute scattering intensity required for quantitative analysis of domain compositions, volume fraction, or interfacial structure. Here, a novel technique to calibrate RSOXS to an absolute intensity at the carbon absorption edge is introduced. It is shown that the X-ray fluorescence from a thin polymer film can be utilized as an angle-independent scattering standard. Verification of absolute intensity is then accomplished through measuring the Flory-Huggins interaction parameter in a phase-mixed polymer melt. The necessary steps for users to reproduce this intensity calibration in their own experiments to improve the scientific output from RSOXS measurements are discussed.

Probing the pathways of free charge generation in organic bulk heterojunction solar cells.

The fact that organic solar cells perform efficiently despite the low dielectric constant of most photoactive blends initiated a long-standing debate regarding the dominant pathways of free charge formation. Here, we address this issue through the accurate measurement of the activation energy for free charge photogeneration over a wide range of photon energy, using the method of time-delayed collection field. For our prototypical low bandgap polymer:fullerene blends, we find that neither the temperature nor the field dependence of free charge generation depend on the excitation energy, ruling out an appreciable contribution to free charge generation though hot carrier pathways. On the other hand, activation energies are on the order of the room temperature thermal energy for all studied blends. We conclude that charge generation in such devices proceeds through thermalized charge transfer states, and that thermal energy is sufficient to separate most of these states into free charges.

Spectral Analysis for Resonant Soft X-Ray Scattering Enables Measurement of Interfacial Width in 3D Organic Nanostructures.

Interfaces are of critical importance to many materials and phenomena yet are difficult to probe. This difficulty is compounded in three-dimensional nanostructures and with delicate organic materials. Here we demonstrate a quantitative spectral analysis of resonant soft x-ray scattering that can accurately measure properties of buried nonplanar interfaces within polymeric systems. We measure the scattering invariant on an absolute scale to quantify the interfacial volume and width involved in mixing at the interface of block copolymer nanostructures. Using continuous contrast tuning, this spectral analysis enables the separation and identification of any number of unique scatterers in complex nanostructures.