The Role of Processing Solvent on Morphology Optimization for Slot-Die Printed Organic Photovoltaics
Not provided.
Polymer Science↗
Engineering topics
Zhu, Lei
Publications and source records attributed to Zhu, Lei.
Surface Charge and Nanoparticle Chromophore Coupling to Achieve Fast Exciton Quenching and Efficient Charge Separation in Photoacoustic Imaging (PAI) and Photothermal therapy (PTT)
Abstract An organic semiconductor nanoparticle (OSN) with surface charge strategy is proposed, which displays excellent photothermal conversion performance. The donor–acceptor hybrid organic semiconductor Y6 is selected as a photothermal chromophore into nanoparticle by self‐assembly, which affords long wavelength absorption, sub‐bandgap emission, and high photon‐to‐thermal conversion. Y6 in OSN adopts closed packing comparing to that in single crystal. The surface charge in OSN causes super‐quenching of the photon excitons, which enhances the nonradiative transition to improve photothermal effect. Lower energy level electronic states are created, which breaks up the bandgap limit and leads to long wavelength emission over 1100 nm. Photothermal therapy and photoacoustic imaging are applied successfully, indicating the success of the new methodology in designing photothermal conversion materials.
Pharmacology & Pharmacy↗
Concept of Operations of Next-Generation Traffic Control Utilizing Infrastructure-Based Cooperative Perception
This paper provides a system architecture for an infrastructure-based cooperative perception fusion engine for next-generation traffic control. This engine will provide a complete state-space digital representation with measurable accuracy to support a wide-range of applications. The architecture includes inputs, functional flow, data standardization recommendations, outputs, and supported applications. The cooperative perception engine addresses critical needs with respect to accelerating the benefits of automation through intelligent roadway infrastructure, which complements and accelerates connected and automated vehicle (CAV) technology. The cooperative perception acquires and fuses information from sensors (radar, LiDAR, and cameras) and CAVs to perceive roadway traffic states of moving objects, creates a complete 3D digital representation of that state-space, and communicates it to downstream application such as intelligent signal control, safety and energy applications, and cooperate driving applications. The intelligent roadway infrastructure approach, as opposed to a vehicle-centric approach, is more scalable because it can be deployed to the roughly 300,000 signalized intersections more readily than over 300 million vehicles in the United States, and accrues early-stage benefits equitable to all roadway users addressing safety, equity, fuel efficiency, and greenhouse gas reduction.
ADVANCED PROPULSION SYSTEMS↗
Smectic C Self‐Assembly in Mesogen‐Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl‐Branched Side Chains
Abstract To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization ( P s ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low P s . In this work, mesogen‐free, chiral polyethers containing sulfonylated methyl‐branched alkyl side chains with a (CH 2 ) 3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n ‐alkyl side chains, the methyl‐branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement–electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole–dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole–dipole interaction to achieve ferroelectricity in these mesogen‐free liquid crystalline polymers.
36 MATERIALS SCIENCE↗
Design Rules of the Mixing Phase and Impacts on Device Performance in High-Efficiency Organic Photovoltaics
In nonfullerene acceptor- (NFA-) based solar cells, the exciton splitting takes place at both domain interface and donor/acceptor mixture, which brings in the state of mixing phase into focus. The energetics and morphology are key parameters dictating the charge generation, diffusion, and recombination. It is revealed that tailoringthe electronic properties of the mixing region by doping with larger-bandgap components could reduce the density of state but elevate the filling state level, leading to improved open-circuit voltage ( V OC ) and reduced recombination. The monomolecular and bimolecular recombinations are shown to be intercorrelated, which show a Gaussian-like relationship with V OC and linear relationship with short-circuit current density ( J SC ) and fill factor (FF). The kinetics of hole transfer and exciton diffusion scale with J SC similarly, indicating the carrier generation in mixing region and crystalline domain are equally important. From the morphology perspective, the crystalline order could contribute to V OC improvement, and the fibrillar structure strongly affects the FF. These observations highlight the importance of the mixing region and its connection with crystalline domains and point out the design rules to optimize the mixing phase structure, which is an effective approach to further improve device performance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Relationships between Cloud Droplet Spectral Relative Dispersion and Entrainment Rate and Their Impacting Factors
Cloud microphysical properties are significantly affected by entrainment and mixing processes. However, it is unclear how the entrainment rate affects the relative dispersion of cloud droplet size distribution. Previously, the relationship between relative dispersion and entrainment rate was found to be positive or negative. To reconcile the contrasting relationships, the Explicit Mixing Parcel Model is used to determine the underlying mechanisms. When evaporation is dominated by small droplets, and the entrained environmental air is further saturated during mixing, the relationship is negative. However, when the evaporation of big droplets is dominant, the relationship is positive. Whether or not the cloud condensation nuclei are considered in the entrained environmental air is a key factor as condensation on the entrained condensation nuclei is the main source of small droplets. However, if cloud condensation nuclei are not entrained, the relationship is positive. If cloud condensation nuclei are entrained, the relationship is dependent on many other factors. High vertical velocity, relative humidity of environmental air, liquid water content, and low droplet number concentration are more likely to cause the negative relationship since new saturation is easier to achieve by evaporation of small droplets. Further, the signs of the relationship are not strongly affected by the turbulence dissipation rate, but the higher dissipation rate causes the positive relationship more significant for a larger entrainment rate. A conceptual model is proposed to reconcile the contrasting relationships. This work enhances the understanding of relative dispersion and lays a foundation for the quantification of entrainment-mixing mechanisms.
54 ENVIRONMENTAL SCIENCES↗
The Crystalline Behavior and Device Function of Nonfullerene Acceptors in Organic Solar Cells
The current research investigates the structure features and intermolecular interactions of nonfullerene acceptors (NFAs) in single crystal and thin films, as well as their solar cell applications. Guiding parameters and key intermolecular forces that lead to 2D brickwork or 3D web packing are identified. The atomic modification is shown as the key to induce hydrogen bonding or π–π stacking column, which results in different crystalline packing. The molecular assembly in thin film is initiated by hydrogen bonding and completed by π–π stacking reorganization. The packing energy is seen as a guiding parameter that dictates the NFA crystalline morphology in blended thin films. The crystalline packing motif is not directly related with device efficiency. However, the crystalline morphology is the key parameter to influence exciton/carrier dynamics and device performance. In conclusion, a broader picture on the scaling behavior of organic semiconductor crystals ranging from oligoacenes to NFAs is established.
14 SOLAR ENERGY↗
Spontaneous carrier generation and low recombination in high-efficiency non-fullerene solar cells
The current research reveals the unique photo physical properties and carrier generation mechanisms of high efficiency non-fullerene acceptor-based organic photovoltaic blends. The analysis of device performance, morphology, and photo physics reveals that the interface carrier generation cannot support the device's current output. It is seen that primary photon excitons can dissociate into charge carriers in Y6, which displays a time scale of ∼0.3 ps with polaron yields above 28% in neat and blended thin films. This characteristic in combination with a large exciton diffusion length enables high morphology tolerance in Y6-overloaded blends. The carrier generation process is also combined with recombination studies. The recombination rate quantified by flux-dependent transient absorption measurements yields less than 5% total recombination and nearly 0% geminate recombination. Furthermore, these results define the advantages of the Y6 non-fullerene acceptor (NFA) and reveal the fundamental importance of developing new NFA materials with superior photo physical properties.
14 SOLAR ENERGY↗
Concept of Operations of Next-Generation Traffic Control Utilizing Infrastructure-Based Cooperative Perception: Preprint
This paper puts forth a system architecture for an infrastructure-based cooperative perception (CP) fusion engine, to provide a complete state-space digital representation, with measurable accuracy, to support a wide-range of applications. The architecture includes the inputs, functional flow, data standardization recommendations, outputs and supported applications. The CP engine addresses critical needs with respect to accelerating the benefits of automation through intelligent roadway infrastructure (IRI), that complements and accelerates connected and automated vehicle (CAV) technology. that the CP acquires and fuses information from sensors (radar, LiDAR, and cameras), and CAVs to intelligently perceive roadway traffic states of all moving objects, create a complete three-dimensional digital representation of that state-space, and communicate it to downstream application such as intelligent signal control, safety and energy applications, and cooperate driving applications for CAVs as examples. The IRI approach, as opposed to a vehicle centric approach, is found to be more scalable in that it can deployed to the roughly 300,000 signalized intersections more readily than the over 300 million vehicles in the US, and accrues early-stage benefits equitable to all roadway users addressing safety, equity, fuel efficiency, and GHG reduction.
ADVANCED PROPULSION SYSTEMS↗
Hard-to-soft transition-enhanced piezoelectricity in poly(vinylidene fluoride) via relaxor-like secondary crystals activated by high-power ultrasonication
We report although high piezoelectric coefficients have recently been observed in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] random copolymers, they have low Curie temperatures, which makes their piezoelectricity thermally unstable. It has been challenging to achieve high piezoelectric performance from the more thermally stable PVDF homopolymer. In this report, we describe how high-power ultrasonic processing was used to induce a hard-to-soft piezoelectric transition and improve the piezoelectric coefficient d 31 in neat PVDF. After high-power ultrasonication for 20 min, a uniaxially stretched and poled PVDF film exhibited a high d 31 of 50.2 ± 1.7 pm V -1 at room temperature. Upon heating to 65 °C, the d 31 increased to a maximum value of 76.2 ± 1.2 pm V -1 , and the high piezoelectric performance persisted up to 110 °C. The enhanced piezoelectricity was attributed to the relaxor-like secondary crystals in the oriented amorphous fraction, broken off from the primary crystals by ultrasonication, as suggested by differential scanning calorimetry and broadband dielectric spectroscopy studies.
relaxor-like secondary crystals↗
Influences of an entrainment–mixing parameterization on numerical simulations of cumulus and stratocumulus clouds
Abstract. Different entrainment–mixing processes can occur in clouds; however, a homogeneous mixing mechanism is often implicitly assumed in most commonly used microphysics schemes. Here, we first present a new entrainment–mixing parameterization that uses the grid mean relative humidity without requiring the relative humidity of the entrained air. Then, the parameterization is implemented in a microphysics scheme in a large eddy simulation model, and sensitivity experiments are conducted to compare the new parameterization with the default homogeneous entrainment–mixing parameterization. The results indicate that the new entrainment–mixing parameterization has a larger impact on the number concentration, volume mean radius, and cloud optical depth in the stratocumulus case than in the cumulus case. This is because inhomogeneous and homogeneous mixing mechanisms dominate in the stratocumulus and cumulus cases, respectively, which is mainly due to the larger turbulence dissipation rate in the cumulus case. Because stratocumulus clouds break up during the dissipation stage to form cumulus clouds, the effects of this new entrainment–mixing parameterization during the stratocumulus dissipation stage are between those during the stratocumulus mature stage and the cumulus case. A large aerosol concentration can enhance the effects of this new entrainment–mixing parameterization by decreasing the cloud droplet size and evaporation timescale. The results of this new entrainment–mixing parameterization with grid mean relative humidity are validated by the use of a different entrainment–mixing parameterization that uses parameterized entrained air properties. This study sheds new light on the improvement of entrainment–mixing parameterizations in models.
54 ENVIRONMENTAL SCIENCES↗
Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene
The homoleptic zinc(II) complex of [2,8-di(1-naphthylethynyl) 3,7-diphenyl 1,9-(4-hexylphenyl)azadipyrromethene (ZnL2) 2 ] is a promising non-planar non-fullerene acceptor for organic photovoltaic applications, but it has a relatively low electron mobility that may limit its performance. Here, we explored the fluorination of peripheral aryl groups to increase intermolecular cofacial π–π stacking interactions, which are desirable for electron transport. Here complexes with fluorine on the distal phenyls [Zn(1F-L2) 2 ], on the naphthyls [Zn(2F-L2) 2 ], and on both [Zn(3F-L2) 2 ] were synthesized and characterized. All three complexes had similar optical and electrochemical properties. The crystal packing structure of Zn(2F-L2) 2 and Zn(3F-L2) 2 revealed cofacial parallel-displaced π–π stacking between the fluorinated 1-naphthylethynyl groups. Such a cofacial orientation was not observed in Zn(L2) 2 crystals, suggesting that fluorination of the naphthyl groups promotes the cofacial π–π stacking orientation. The hole mobility increased from 1.0 × 10 –4 cm 2 V –1 s –1 for Zn(L2) 2 to 0.8–1.0 × 10 –3 cm 2 V –1 s –1 for the fluorinated complexes. Fluorination on the naphthyl groups increased the electron mobility from 4.2 × 10 –5 cm 2 V –1 s –1 for Zn(L2) 2 and Zn(1F-L2) 2 to 2.0 × 10 –4 cm 2 V –1 s –1 for Zn(2F-L2) 2 and Zn(3F-L2) 2 , consistent with cofacial π–π stacking being favorable for electron transport. The three complexes were tested in OPVs using regioregular poly(3-hexylthiophene) (P3HT) as the p-type material, and the best power conversion efficiencies were 5.2, 5.4, and 5.8% for Zn(2F-L2) 2 , Zn(1F-L2) 2 , and Zn(3F-L2) 2 , respectively, compared to 5.5% for Zn(L2) 2 . The fluorination combination found in Zn(3F-L2) 2 resulted in the best device performance. This study points to a viable strategy to increase the electron mobility and performance of non-planar zinc(II) complexes of azadipyrromethene.
36 MATERIALS SCIENCE↗
Mappymatch FKA: YAMM (Yet Another Map-Matcher) [SWR 22-38]
A surprisingly non-trivial technical challenge is to associate points in space (e.g., GPS data) with specific segments of a road network or map. The software package ( allows users to match GPS point data to a road network (commonly known as "map matching"). The software is designed such that a user could match a set of GPS points to a variety of different road network representations using a variety of map matching algorithms. There are currently several "built-in" road networks and map matching algorithms but the software has been designed to enable new ones to be added with minimal overhead.
Reinicke, Nicholas↗
Mappymatch [SWR 22-38]
Mappymatch is a pure-python package developed and open sourced by the National Renewable Energy Laboratory. It contains a collection of "Matchers" that enable matching a GPS trace (series of GPS coordinates) to a map. As of 8/14/2023, The current matchers are: LCSSMatcher: A matcher that implements the LCSS algorithm described in this paper. Works best with high resolution GPS traces. OsrmMatcher: A light matcher that pings an OSRM server to request map matching results. See the official documentation for more info. ValhallaMatcher: A matcher to ping a Valhalla server for map matching results. Currently supported map formats are: Open Street Maps NOTE: This software was formerly known as YAMM (Yet Another Map-Matcher)
Reinicke, Nicholas↗
Siloxane-functional small molecule acceptor for high-performance organic solar cells with 16.6% efficiency
As one of the simple but most effective molecular design strategies, side-chain engineering has been widely employed to modify the photoelectric properties of active layer materials for boosting the photovoltaic performance of organic solar cells (OSCs). In this work, a functionalized small molecule acceptor (SMA) named BTSi-4F with a bulky siloxane-terminated solubilizing group as side-chains, derived from a classical SMA of Y6, was designed and synthesized. The results demonstrate that the introduction of siloxane-functional terminated groups into SMA not only affects the optical absorption and molecular energy levels, but also regulates the miscibility between the polymer donor and SMA. Compared to the original Y6, BTSi-4F exhibits a better solubility, upshifted lowest unoccupied molecular orbital (LUMO) energy level, more ordered molecular packing, and higher electron-mobility. Matched with a wide bandgap polymer donor PM6, the chlorobenzene-processed OSCs based on PM6:BTSi-4F achieved a superior power conversion efficiency (PCE) of 16.6% with both high open-circuit voltage (V oc ) of 0.90 V and high fill factor (FF) of 0.77, while the devices based on PM6:Y6 obtained a much lower PCE of 13.0% with a V oc of 0.81 V and FF of 0.69 under the same conditions. This work offers a promising molecular design strategy of siloxane-terminated side chain engineering to develop high-performance SMAs for efficient OSCs.
14 SOLAR ENERGY↗
Relaxor ferroelectric polymer exhibits ultrahigh electromechanical coupling at low electric field
Electromechanical (EM) coupling—the conversion of energy between electric and mechanical forms—in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. Here, we introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it. Under a low–dc bias field of 40 megavolts per meter, the relaxor tetrapolymer has an EM coupling factor (k 33 ) of 88% and a piezoelectric coefficient (d 33 ) >1000 picometers per volt. These values make this solution-processed polymer competitive with ceramic oxide piezoelectrics, with the potential for use in distinct applications.
36 MATERIALS SCIENCE↗