Molecular Weight-Independent "Polysoap" Nanostructure Characterized via In Situ Resonant Soft X-ray Scattering.

Studying polymer micelle structure and loading dynamics under environmental conditions is critical for nanocarrier applications but challenging due to a lack of in situ nanoprobes. Here, the structure and loading of amphiphilic polyelectrolyte copolymer micelles, formed by 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and n-dodecyl acrylamide (DDAM), were investigated using a multimodal approach centered around in situ resonant soft X-ray scattering (RSoXS). We observe aqueous micelles formed from polymers of wide-ranging molecular weights and aqueous concentrations. Despite no measurable critical micelle concentration (CMC), structural analyses point toward multimeric structures for most molecular weights, with the lowest molecular weight micelles containing mixed coronas and forming loose micelle clusters that enhance hydrocarbon uptake. The sizes of the micelle substructures are independent of both the concentration and molecular weight. Combining these results with a measured molecular weight-invariant surface charge and zeta potential strengthens the link between the nanoparticle size and ionic charge in solution that governs the polysoap micelle structure. Such control would be critical for nanocarrier applications, such as drug delivery and water remediation.

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.

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.

A NIST facility for resonant soft x-ray scattering measuring nano-scale soft matter structure at NSLS-II.

We present the design and performance of a polarized resonant soft x-ray scattering (RSoXS) station for soft matter characterization built by the national institute of standards and technology at the national synchrotron light source-II (NSLS-II). The RSoXS station is located within the spectroscopy soft and tender beamline suite at NSLS-II located in Brookhaven national laboratory, New York. Numerous elements of the RSoXS station were designed for optimal performance for measurements on soft matter systems, where it is of critical importance to minimize beam damage and maximize collection efficiency of polarized x-rays. These elements include a novel optical design, sample manipulator and sample environments, as well as detector setups. Finally, we will report the performance of the measurement station, including energy resolution, higher harmonic content and suppression methods, the extent and mitigation of the carbon absorption dip on optics, and the range of polarizations available from the elliptically polarized undulator source.

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.

Quantitative relations between interaction parameter, miscibility and function in organic solar cells.

Although it is known that molecular interactions govern morphology formation and purity of mixed domains of conjugated polymer donors and small-molecule acceptors, and thus largely control the achievable performance of organic solar cells, quantifying interaction-function relations has remained elusive. Here, we first determine the temperature-dependent effective amorphous-amorphous interaction parameter, χaa(T), by mapping out the phase diagram of a model amorphous polymer:fullerene material system. We then establish a quantitative 'constant-kink-saturation' relation between χaa and the fill factor in organic solar cells that is verified in detail in a model system and delineated across numerous high- and low-performing materials systems, including fullerene and non-fullerene acceptors. Our experimental and computational data reveal that a high fill factor is obtained only when χaa is large enough to lead to strong phase separation. Our work outlines a basis for using various miscibility tests and future simulation methods that will significantly reduce or eliminate trial-and-error approaches to material synthesis and device fabrication of functional semiconducting blends and organic blends in general.

Monitoring Charge Separation Processes in Quasi-One-Dimensional Organic Crystalline Structures.

We perform the transient absorption spectroscopy experiments to investigate the dynamics of the low-energy collective electron-hole excitations in α-copper phthalocyanine thin films. The results are interpreted in terms of the third-order nonlinear polarization response function. It is found that, initially excited in the molecular plane, the intramolecular Frenkel exciton polarization reorients with time to align along the molecular chain direction to form coupled Frenkel-charge-transfer exciton states, the eigenstates of the one-dimensional periodic molecular lattice. The process pinpoints the direction of the charge separation in α-copper phthalocyanine and similar organic molecular structures. Being able to observe and monitor such processes is important both for understanding the physical principles of organic thin film solar energy conversion device operation and for the development of organic optoelectronics in general.

Intrinsic Charge Trapping Observed as Surface Potential Variations in diF-TES-ADT Films.

Spatial variations in surface potential are measured with Kelvin probe force microscopy for thin films of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophenes (diF-TES-ADT) grown on SiO2 and silane-treated SiO2 substrates by organic molecular beam deposition. The variations are observed both between and within grains of the polycrystalline organic film and are quantitatively different than electrostatic variations on the substrate surfaces. The skewness of surface potential distributions is larger on SiO2 than on HMDS-treated substrates. This observation is attributed to the impact of substrate functionalization on minimizing intrinsic crystallographic defects in the organic film that can trap charge.

High-Performance Non-Fullerene Polymer Solar Cells Based on a Pair of Donor-Acceptor Materials with Complementary Absorption Properties.

A 7.3% efficiency non-fullerene polymer solar cell is realized by combining a large-bandgap polymer PffT2-FTAZ-2DT with a small-bandgap acceptor IEIC. The complementary absorption of donor polymer and small-molecule acceptor is responsible for the high-performance of the solar-cell device. This work provides important guidance to improve the performance of non-fullerene polymer solar cells.

Tuning Open-Circuit Voltage in Organic Solar Cells with Molecular Orientation.

The role of molecular orientation of a polar conjugated polymer in polymer-fullerene organic photovoltaic (OPV) cells is investigated. A planar heterojunction (PHJ) OPV cell composed of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) is used as a model system to isolate the effect of the interfacial orientation on the photovoltaic properties. The molecular orientation of the aggregate P3HT relative to the PCBM layer is varied from highly edge-on (conjugated ring plane perpendicular to the interface plane) to appreciably face-on (ring plane parallel to the interface). It is found that as the P3HT stacking becomes more face-on there is a positive correlation to the OPV open-circuit voltage (V(OC)), attributed to a shift in the highest occupied molecular orbital (HOMO) energy level of P3HT. In addition, the PHJ OPV cell with a broad P3HT stacking orientation distribution has a V(OC) comparable to an archetypal bulk heterojunction (BHJ) device. These results suggest that, in the BHJ OPV cell, the hole energy level in the charge transfer state is defined in part by the orientation distribution of the P3HT at the interface with PCBM. Finally, the photoresponses of the devices are also shown to have a dependence on P3HT stacking orientation.

Mobility-controlled performance of thick solar cells based on fluorinated copolymers.

Developing novel materials and device architectures to further enhance the efficiency of polymer solar cells requires a fundamental understanding of the impact of chemical structures on photovoltaic properties. Given that device characteristics depend on many parameters, deriving structure-property relationships has been very challenging. Here we report that a single parameter, hole mobility, determines the fill factor of several hundred nanometer thick bulk heterojunction photovoltaic devices based on a series of copolymers with varying amount of fluorine substitution. We attribute the steady increase of hole mobility with fluorine content to changes in polymer molecular ordering. Importantly, all other parameters, including the efficiency of free charge generation and the coefficient of nongeminate recombination, are nearly identical. Our work emphasizes the need to achieve high mobility in combination with strongly suppressed charge recombination for the thick devices required by mass production technologies.