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1. Rapid stress relaxation of high‐ T _g conjugated polymeric thin films

   https://doi.org/10.1002/pol.20230671  

   Ma, Guorong; Zhang, Song; Galuska, Luke_A; Gu, Xiaodan (November 2023, Journal of Polymer Science)

   Abstract Conjugated polymers consist of complex backbone structures and side‐chain moieties to meet various optoelectronic and processing requirements. Recent work on conjugated polymers has been devoted to studying the mechanical properties and developing new conjugated polymers with low modulus and high‐crack onset strain, while the thin film mechanical stability under long‐term external tensile strain is less investigated. Here we performed direct mechanical stress relaxation tests for both free‐standing and thin film floated on water surface on both high‐T_gand low‐T_gconjugated polymers, as well as a reference nonconjugated sample, polystyrene. We measured thin films with a range of film thickness from 38 to 179 nm to study the temperature and thickness effect on thin film relaxation, where an apparent enthalpy–entropy compensation effect for glassy polymer PS and PM6 thin films was observed. We also compared relaxation times across three different conjugated polymers and showed that both crystalline morphology and higher modulus reduce the relaxation rate besides higher glass transition temperature. Our work provides insights into the mechanical creep behavior of conjugated polymers, which will have an impact on the future design of stable functional organic electronics. 

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2. Hafnium boosts charge carrier dynamics in hematite for improved solar water splitting

   https://doi.org/10.1016/j.matlet.2023.134176  

   Morishita, Gustavo M.; Rodríguez-Gutiérrez, Ingrid; Castro, Ricardo H.R.; Souza, Flavio L. (June 2023, Materials Letters)

   The work demonstrates a three-fold increase in photoelectrochemical efficiency of hematite nanorods as a result of the combination of Hafnium surface doping and the incorporation of a ZrO2 underlayer on FTO. While the ZrO2 layer reduced the electron loss from the back-injection into the FTO contact support, Hafnium surface doping did not significantly alter the hematite lattice structure. But rather, Hafnium induced nanorod diameter reduction from 32 ± 2 and 26 ± 2 nm, with a consequent increase in the active surface area. The linear sweep voltammetry measurements with 100 mW cm−2 illumination in a 500 nm photoanode thickness showed a photocurrent density of 2.07 mA cm−2 at 1.23 V in a reversible hydrogen electrode (RHE). The value contrasts with the bare hematite rods (0.75 mA cm−2), highlighting the photoanode design's role in improving solar power hydrogen production. 

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3. Bromide Causes Facet-Selective Atomic Addition in Gold Nanorod Syntheses

   https://doi.org/10.1021/acs.chemmater.0c01494  

   Brown, Micah; Wiley, Benjamin J. (January 2020, Chemistry of Materials)

   The aspect ratio-dependent properties of gold nanorods are used in a variety of applications, but the cause of anisotropic nanorod growth remains unclear. Measurements utilizing single-crystal electrodes were collected to determine what additive(s) in pentatwinned gold nanorod syntheses are responsible for facet-selective atomic addition. With cetyltrimethylammonium in the absence of bromide, the rate of atomic addition to Au(100) and Au(111) single crystals was the same, and isotropic nanoparticles were produced. The addition of increasing concentrations of bromide suppressed the rate of atomic addition to Au(100) relative to Au(111) and increased the aspect ratio of gold nanorods. Bromide was a more effective passivator of Au(100) in the absence of cetyltrimethylammonium, indicating cetyltrimethylammonium does not cause facet-selective atomic addition. Cetyltrimethylammonium surfactant is still necessary for gold nanorod growth because it reduces the rate of gold ion reduction and stabilizes suspended nanoparticles against aggregation. 

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4. Ultrafast Study of Excited State Dynamics of Amino Metal Halide Molecular Clusters

   https://doi.org/10.1021/acs.jpclett.3c01952  

   Zhang, Heng; Zeitz, David C; Zhang, Jin Z (September 2023, The Journal of Physical Chemistry Letters)

   The excited state dynamics of ligand-passivated PbBr2 molecular clusters (MCs) in solution have been investigated for the first time using femtosecond transient absorption spectroscopy. The results uncover a transient bleach (TB) feature peaked around 404 nm, matching the ground state electronic absorption band peaked at 404 nm. The TB recovery signal can be fitted with a triple exponential with fast (10 ps), medium (350 ps), and long (1.8 ns) time constants. The medium and long time constants are very similar to those observed in the timeresolved photoluminescence (TRPL) decay monitored at 412 nm. The TB fast component is attributed to vibrational relaxation in the excited electronic state while the medium component with dominant amplitude is attributed to recombination between the relaxed electron and hole. The small amplitude slow component is assigned to electrons in a relatively long-lived excited electronic state, e.g., triplet state, or shallow trap state due to defects. This study provides new insights into the excited state dynamics of metal halide MCs. 

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5. Nanorod position and orientation in vertical cylinder block copolymer films

   https://doi.org/10.1039/d0sm00043d  

   Rasin, Boris; Lindsay, Benjamin J.; Ye, Xingchen; Meth, Jeffrey S.; Murray, Christopher B.; Riggleman, Robert A.; Composto, Russell J. (March 2020, Soft Matter)

   The self-assembly of gold nanorods (AuNRs) of different sizes with a block copolymer (BCP) is studied. Polystyrene- block -poly(2-vinylpyridine) (PS- b -P2VP) films containing P2VP functionalized AuNRs are solvent annealed resulting in a BCP morphology of vertical P2VP cylinders in a PS matrix. At the surface of the PS- b -P2VP films long AuNRs are found in the bridging and vertical states. The bridging state is where the long axis of the AuNR is parallel to the film surface, the AuNR is embedded in the film, and each end of the AuNR is at the top of nearest neighbor P2VP cylinders. The vertical state is where the AuNR is localized within a vertical P2VP cylinder, the AuNR long axis is perpendicular to the film surface and the upper tip of the AuNR is at the film surface. Short AuNRs were found in the bridging and vertical states as well as in a state not observed for the long AuNRs, the centered state. The centered state is where an AuNR has its long axis parallel to the film surface, is embedded in the film, and is centered over a vertical P2VP cylinder. Hybrid particle-field theory (HPFT) simulations modeling the experimental system predict that for the long AuNRs only the bridging state should be observed while for the short AuNRs only the bridging and centered states should be observed. Possible explanations for why the vertical state is observed in experiments despite being thermodynamically unfavorable in simulations are discussed. HPFT simulations also show that when a nanorod is in the bridging state the two cylinders it bridges remain intact and extend from the nanorod to the substrate. Further, the minority block of the BCP is shown to wet the bottom of the bridging nanorod. The bridging state is very promising for the future development of self-assembled nanoscale devices. 

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