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Properties of Charged Conjugated Polymers Deposited by Electrospraying on Substrates with an Insulating Oxide Layer

Anmol Arya, Solomon L. Joseph, Francois Vonau, Jean-Luc Bubendorff, Silvia Siegenführ, Laurent Simon, Günter Reiter. J. Phys. Chem. C, published online

In the course of electrospraying in a vacuum, polymers acquire electric charges, which are distributed along their backbone. Here, we demonstrate that these charges have a strong impact on the molecular ordering and spectroscopic properties of conjugated polymers when deposited on substrates with an insulating oxide layer. To this end, we electrosprayed varying amounts of poly(3-hexylthiophene) (P3HT) onto silicon substrates with oxide layers of different thickness. The resulting morphologies were explored by atomic force microscopy. The corresponding spectroscopic properties, including their changes in time upon illumination, were derived from photoluminescence (PL) measurements. On insulating substrates, charges were retained on the polymer chains, causing long-range electrostatic repulsion and the formation of largely separated droplet-like objects containing multiple chains. These objects exhibited significant PL intensities for photons with a wavelength (λ) less than ca. 600 nm, suggesting the lack of π–π stacking interactions between P3HT chains. (more...)


Reversible Metamorphosis of a Conjugated Polymer Induced by Photoexcitation

Solomon Joseph, Anmol Arya, Günter Reiter. Advanced Photonics Research 7 (2026) e202500311

Optoelectronic properties of materials are frequently examined through spectroscopic tools based on the absorption and emission of (visible) photons. Typically, one assumes that these transient characterization processes do not cause observable change of these properties because of the low power of the employed light sources. However, for flexible conjugated polymers in a medium of low viscosity, it is decidedly unclear whether photoexcitation of electrons on the backbone of a long polymer chain has an influence on macromolecular conformations and the corresponding intermolecular interactions. Here, we provide clear experimental evidence that continuous absorption of photons progressively causes persistent changes in the spectroscopic properties of conjugated polymers, accompanied by microscopically observable changes in their spatial distribution within a low-viscosity matrix. By contrast, all these changes were completely absent in nonilluminated parts of the same sample.(more...)


Temperature dependence of crystal – melt coexistence for supported polyethylene filaments

Da Huang, Thorsten Hugel, Bizan N. Balzer, Günter Reiter. Nature Communications 16 (2025) 11127

The broken symmetry of molecular interactions at interfaces is causing that crystals are often covered by a thin liquid layer of their own melt. Such crystal–melt coexistence can be related to phenomena of surface premelting, secondary nucleation and melting point depression, particularly important for small systems. Here, we employed intermittent-contact mode atomic force microscopy imaging on nanoscopic semi-cylindrical filaments of polyethylene on a substrate to observe that these filaments contained a crystalline core bounded by molten regions of rather uniform width,  W_soft= (9 ± 2) nm at room temperature, which increased reversibly with temperature T. Filaments smaller than ca. 2∙W_soft (T) were completely molten. The values of W_soft (T) compared favorably with theoretically predicted characteristic length scales in the context of nucleation, surface premelting and the melting point depression of finite size crystals. Altogether, we show that these three phenomena are related and dominated by the intermolecular forces acting at crystal surfaces. (more...)
 

Liste der Veröffentlichungen

How Chain-Folding Crystal Growth Determines Thermodynamic Stability of Polymer Crystals
Xiaoming Jiang, Günter Reiter, Wenbing Hu. J. Phys. Chem. B, 120 (2016) 566–571
Stabilization of nuclei of lamellar polymer crystals: Insights from a comparison of the Hoffman-Weeks line with the crystallization line
Jun Xu, Barbara Heck, Hai-Mu Ye, Jing Jiang, Yi-Ren Tang, Jin Liu, Bao-Hua Guo, Renate Reiter, Dongshan Zhou, Günter Reiter. Macromolecules 49 (2016) 2206–2215
Role of Preparation Pathways and Tacticity on the Non-Equilibrium Dynamcis of Polystyrene Films
Rishab Handa. Master Thesis im Studiengang M.Sc. Sustainable Materials, 2016
Variation of the contact resistance with electric current for gold electrodes on a squaraine single crystal
Leonid Govor, Guenter Reiter, and Jurgen Parisi. Phys. Status Solidi A 212 (2015) 2738–2746, DOI 10.1002/pssa.201532241
Simulation of secondary nucleation of polymer crystallization via a model of microscopic kinetics
Kun-Lun Xu, Bao-Hua Guo, Renate Reiter, Günter Reiter, Jun Xu. Chinese Chemical Letters 26, 1105–1108 (2015) / DOI: 10.1016/j.cclet.2015.06.002
From holes to drops to toroids: Conditions for the transcription of surface patterns into three-dimensional morphologies via rim instabilities in the course of dewetting
Samer Al Akhrass, Laurent Vonna and Günter Reiter. In: Polymer Surfaces in Motion: Unconventional Patterning Methods, Eds. Juan Rodriguez-Hernandez and Carlos Drummond. Springer 2015
Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States
Sivasurender Chandran, Stefanie Dold, Amaury Buvignier, Kai-Steffen Krannig, Helmut Schlaad, Günter Reiter, and Renate Reiter. Langmuir 2015, 31, 6426−6435. DOI: 10.1021/acs.langmuir.5b01212
High Temperature Stability of Dewetting-Induced Thin Polyethylene Filaments
Bin Zhang, Jingbo Chen, Paul Freyberg, Renate Reiter, Rolf Mülhaupt, Jun Xu, Günter Reiter. Macromolecules 48, 1518–1523 (2015)
Triangular dewetting by symmetry breaking in blends of stiff and flexible polymers
Paul Freyberg. Inaugural-Dissertation zur Erlangung des Doktorgrades der Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2015
Conductive atomic force microscopy measurements on organic nanocrystals
Sven Renkert. Master Thesis, Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2014
The influence of the additive composition on degradation induced changes in poly(ethylene-co-vinyl acetate) during photochemical aging
Angelika Beinert, Cornelia Peike, Ines Dürr, Michael D. Kempe, Günter Reiter, Karl-Anders Weiß. 29th European PV Solar Energy Conference and Exhibition, 22-26 Sept. 2014, Amsterdam, The Netherlands
Wie kristallisieren Polymere?
Gert Strobl. Physik Journal 13, 47-50 (2014)
The Crucial Role of Cadmium Acetate-Induced Conformational Restriction in Microscopic Structure and Stability of Polystyrene-block-Polyvinyl pyridine Thin Films
Feifei Xue, Hongfei Li, Jichun You, Conghua Lu, Günter Reiter, Shichun Jiang. Polymer 55, 5801-5810 (2014)
Molecular Weight Dependent Changes in Morphology of Solution Grown Polyethylene Single Crystals
Bin Zhang, Jingbo Chen, Moritz C. Baier, Stefan Mecking, Renate Reiter, Rolf Mülhaupt, Günter Reiter. Macrom. Rapid Comm. 36, 181-189 (2015)
Annealing-Induced Periodic Patterns in Solution Grown Polymer Single Crystals
Bin Zhang, Jingbo Chen, Hui Zhang, Moritz C. Baier, Stefan Mecking, Renate Reiter, Rolf Mülhaupt, Günter Reiter, RSC Advances 5, 12974 (2015)
Anisotropic Photophysical Properties of Highly Aligned Crystalline Structures of a Bulky Substituted Poly(thiophene)
Yingying Wang, Barbara Heck, Daniel Schiefer, John O. Agumba, Michael Sommer, Tao Wen, and Günter Reiter. ACSMacroLett. 3, 881-885 (2014)
Cellulose nanocrystals’ production in near theoretical yields by 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) – mediated hydrolysis
Jia Mao, Barbara Heck, Günter Reiter, Marie-Pierre Laborie. Carbohydrate Polymers 117, 443–451 (2015)
Correlating polymer crystals via self-induced nucleation
Hui Zhang, Muhuo Yu, Bin Zhang, Renate Reiter, Maximilian Vielhauer, Rolf Mülhaupt, Jun Xu, Günter Reiter. PhysRevLett 112, 237801 (2014)
Nickel Catalyst with a Hybrid P, N Ligand for Kumada Catalyst Transfer Polycondensation of Sterically Hindered Thiophenes
Daniel Schiefer, Tao Wen, Yingying Wang, Pierre Goursot, Hartmut Komber, Ralf Hanselmann, Pierre Braunstein, Günter Reiter, Michael Sommer. ACSMacroLett. 3, 617-621 (2014)
Tunneling Spectroscopy Measurements on Hydrogen-Bonded Supramolecular Polymers
François Vonau, Dominique Aubel, Laurent Bouteiller, Roozbeh Shokri, Günter Reiter, Olga Guskova, Laurent Simon. Nanoscale 6, 8250 (2014)
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