Bartosz Paruzel

Poly(amidoamine) (PAMAM)-based electrolytes are prepared by dissolving the PAMAM half-generations G1.5 or G2.5 in propylene carbonate (PC), either with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) or sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) salts. The solutions, designed for ion battery applications, are studied in terms of ions transport properties. Raman Spectroscopy reveals information about the interactions between cations and PAMAM dendrimers as well as full dissociation of the salts in all solutions. Pulsed-field gradient Nuclear Magnetic Resonance (PFG NMR), measured as a function of both temperature and PAMAM concentration, are obtained for the cation, anion, solvent, and dendrimer molecules using lithium (⁷Li), sodium (²³Na), fluorine (¹⁹F), and hydrogen (¹H) NMR, respectively. It was found that lithium diffusion is slow compared to the larger TFSI anion and decreases with PAMAM concentration due to interactions between cation and dendrimer. Comparison of conductivities calculated from diffusion coefficients using the Nernst–Einstein equation, with conductivity measurements obtained from Impedance Spectroscopy (IS), shows slightly higher IS conductivities, caused among others by PAMAM conductivity.

The paper contributes to the characterization and understanding the mutual interactions of the polar polymer gate dielectric and organic semiconductor in organic field effect transistors (OFETs). It has been shown on the example of cyanoethylated polyvinylalcohol (CEPVA), the high-k dielectric containing strong polar side groups, that the conditions during dielectric layer solidification can significantly affect the charge transport in the semiconductor layer. In contrast to the previous literature we attributed the reduced mobility to the broader distribution of the semiconductor density of states (DOS) due to a significant dipolar disorder in the dielectric layer. The combination of infrared (IR), solid-state nuclear magnetic resonance (NMR) and broadband dielectric (BDS) spectroscopy confirmed the presence of a rigid hydrogen bonds network in the CEPVA polymer. The formation of such network limits the dipolar disorder in the dielectric layer and leads to a significantly narrowed distribution of the density of states (DOS) and, hence, to the higher charge carrier mobility in the OFET active channel made of 6,13-bis(triisopropylsilylethynyl)pentacene. The low temperature drying process of CEPVA dielectric results in the decreased energy disorder of transport states in the adjacent semiconductor layer, which is then similar as in OFETs equipped with the much less polar poly(4-vinylphenol) (PVP). Breaking hydrogen bonds at temperatures around 50 °C results in the gradual disintegration of the stabilizing network and deterioration of the charge transport due to a broader distribution of DOS.

The localized surface plasmon (LSP) photophysical phenomenon occurring in metal nanostructures is often presented as a way to effectively couple light into sub-wavelength-scale photovoltaic devices, which would otherwise suffer from a weak light absorption. The simultaneous complementary effect of localized optical field depletion receives far less attention. We studied a system consisting of a planar gold nanoparticles array (AuNP) deposited at the surface of a semiconducting polymer thin film (P3HT). By comparing the UV-vis spectra of P3HT with and without the AuNP array, we have estimated that the AuNPs screen the optical absorption in the interfacial layer of about 3.8 nm effective thickness due the near-field depletion effect. It suggests that the AuNP array may be used to practically "hide" a thin semiconductor layer, e.g., in order to tune the perceived color of the photovoltaic cell embedded in architecture, or in wearable devices.

We developed a new methodology for determining charge concentration dependent mobility from organic field-effect transistor (OFET) characteristics, applicable for semiconducting polymers with structural and energy disorder. We show that basic formulae recommended by the “IEEE Standard for Test Methods for the Characterization of Organic Transistors and Materials” for the determination of the field-effect mobility as obtained from the slope I_SD ^1/2vs. V_SG (in the saturation regime) or from the transconductance dI_SD/dV_SG (in the linear regime) are not suitable for materials with concentration dependent charge carrier mobility. We propose alternative expressions, which can be directly analytically derived from the drift–diffusion equation with the mobility explicitly dependent on the charge concentration. This methodology for mobility determination was used for analysis of the experimental data obtained for a poly(3-hexylthiophene)-based OFET with the bottom gate–bottom SD electrode configuration.

Localized surface plasmon (LSP) photophysical phenomena occurring in metal nanostructures are often presented as a method to effectively couple light into photovoltaic devices of sub-wavelength-scale thickness. However, the excitation of LSP is also associated with rapid energy dissipation leading to local heating, which affects the excitation energy pathway. We studied a system consisting of a planar gold nanoparticle (AuNP) array deposited at the surface of a semiconducting polymer thin film (P3HT). We observed heat transfer from laser pulse excited AuNPs into the P3HT, which was evidenced as a long-living thermochromic effect on transient optical absorption. By modeling of the ultrafast kinetics of exciton population evolution, we determined that their decay was caused by their mutual annihilation. The decay rate was controlled by a phonon-assisted one-dimensional diffusion mechanism with a diffusion constant of 2.2 nm² ps⁻¹. The transferred heat resulted in an increase of the diffusion constant by a factor of almost 2, compared to the control system of P3HT without AuNPs. These results are of practical use for the design of plasmon-enhanced optoelectronic devices.

There is a big demand for the development of polymer materials for flexible electronics, among them polymers with a high dielectric constant play an important role. Here the preparation and properties of a polymer blend composed of poly(2-cyanoethyl vinyl ether) (CEPVA) as an amorphous polymer with dielectric constant (ε') ~ 15 but glass temperature (Tg) close to room temperature, and poly(methyl methacrylate) (PMMA), a polymer with low ε' ~ 5 and high Tg, are reported. The film forming ability, structure and dielectric properties of the blend are reported to verify its applicability for capacitors and field effect transistors. PMMA:CEPVA ratios 10:90 and 30:70 represent the best composition for obtaining a monophasic system with increased dielectric constant and Tg well above the room temperature. The improved properties have been attributed to the impact of PMMA on the relaxation phenomena of CEPVA, namely to an increased mobility of cyano-groups responsible for the dielectric behavior, as it was observed by the broadband dielectric and nuclear magnetic resonance (NMR) spectroscopies