From Chain- to Graphene-like Hydroxyl-terminated (ZnO)n Clusters with n≤6 Obtained via Zinc Dimethoxide Hydrolysis and Condensation: Ab initio Structural, Electronic, Vibrational and Optical Properties Calculations.

Recent reports are focusing on the structural evolution from the atomic-scale and also at the expenses of alkyl zinc alkoxide precursors towards (ZnO)n clusters and nanostructures with different interesting motifs, but still not much is known about their electronic properties. In this manuscript, we present a theoretical study using DFT and TD-DFT methodologies on the hydrolysis and condensation of zinc dimethoxide precursor in its monomeric, dimeric and trimeric forms towards thermodynamically stable hydroxyl-terminated (ZnO)n clusters with novel chain- and graphene-like fashions. For all cases, distinct vibrational and optical spectra features were assigned evidencing a global monotonic decrease in the opto-electronic gap with increasing oligomerization and cyclization stages. In addition, the electron-affinity of all clusters was also observed to be enhanced with increasing oligomerization and cyclization stages and the electronic charge localization in -e charged clusters was observed to be strongly related to the presence of zinc-oxo subunits and other particular structural features. Our calculations also indicate that the stabilization through hydroxyl termination of both chain- and graphene-like ZnO clusters not only could be a promising driving force to obtain larger atomic-scale 1D and 2D nanostructures but also envisage interesting properties, particularly as electronic acceptor materials for energy applications.

Exploring Mixed Ionic-Electronic-Conducting PVA/PEDOT:PSS Hydrogels as Channel Materials for Organic Electrochemical Transistors.

Here, we report the preparation and evaluation of PVA/PEDOT:PSS-conducting hydrogels working as channel materials for OECT applications, focusing on the understanding of their charge transport and transfer properties. Our conducting hydrogels are based on crosslinked PVA with PEDOT:PSS interacting via hydrogen bonding and exhibit an excellent swelling ratio of ~180-200% w/w. Our electrochemical impedance studies indicate that the charge transport and transfer processes at the channel material based on conducting hydrogels are not trivial compared to conducting polymeric films. The most relevant feature is that the ionic transport through the swollen hydrogel is clearly different from the transport through the solution, and the charge transfer and diffusion processes govern the low-frequency regime. In addition, we have performed in operando Raman spectroscopy analyses in the OECT devices supported by first-principle computational simulations corroborating the doping/de-doping processes under different applied gate voltages. The maximum transconductance (gm~1.05 µS) and maximum volumetric capacitance (C*~2.3 F.cm-3) values indicate that these conducting hydrogels can be promising candidates as channel materials for OECT devices.

On the Donor: Acceptor Features for Poly(3-hexylthiophene): TiO2 Quantum Dots Hybrid Materials Obtained via Water Vapor Flow Assisted Sol-Gel Growth.

Here, we present a novel methodology for the preparation of P3HT:TiO2 quantum dots hybrid materials via water vapor flow-assisted sol-gel growth focusing on the structural, optical and electrical property characterization complemented with first-principles calculations as a promising donor-acceptor system for polymer and hybrid solar cells. X-ray diffraction and UV-Vis spectroscopy analyses suggest that the increasing concentration of TiO2 quantum dots leads to the formation of higher amounts of amorphous regions while the crystalline regions exhibited interesting aspect ratio modifications for the P3HT polymer. Raman spectra evidenced the formation of charge carriers in the P3HT with increasing TiO2 quantum dots content and the P3HT:TiO2 50:50 weight ratio resulted in the best composition for optimizing the bulk electronic conductivity, as evidenced by impedance spectroscopy studies. Our DFT calculations performed for a simplified model of the P3HT:TiO2 interface revealed that there is an important contribution of the thiophene carbon atoms states in the conduction band at the Fermi level. Finally, our DFT calculations also reveal an evident gain of electron density at the TiO2 (101) surface while the thiophene rings showed a loss of the electron density, thus confirming that the P3HT:TiO2 junction acts as a good donor-acceptor system. In our opinion, these results not only present a novel methodology for the preparation of P3HT:TiO2 quantum dots hybrid materials but also reveal some key aspects to guide the more rational design of polymer and hybrid solar cells.

Hybrid Organic-Inorganic Materials and Interfaces With Mixed Ionic-Electronic Transport Properties: Advances in Experimental and Theoretical Approaches.

The main goal of this mini-review is to provide an updated state-of-the-art of the hybrid organic-inorganic materials focusing mainly on interface phenomena involving ionic and electronic transport properties. First, we review the most relevant preparation techniques and the structural features of hybrid organic-inorganic materials prepared by solution-phase reaction of inorganic/organic precursor into organic/inorganic hosts and vapor-phase infiltration of the inorganic precursor into organic hosts and molecular layer deposition of organic precursor onto the inorganic surface. Particular emphasis is given to the advances in joint experimental and theoretical studies discussing diverse types of computational simulations for hybrid-organic materials and interfaces. We make a specific revision on the separately ionic, and electronic transport properties of these hybrid organic-inorganic materials focusing mostly on interface phenomena. Finally, we deepen into mixed ionic-electronic transport properties and provide our concluding remarks and give some perspectives about this growing field of research.

Mini-Review: Mixed Ionic-Electronic Charge Carrier Localization and Transport in Hybrid Organic-Inorganic Nanomaterials.

In this mini-review, a comprehensive discussion on the state of the art of hybrid organic-inorganic mixed ionic-electronic conductors (hOI-MIECs) is given, focusing on conducting polymer nanocomposites comprising inorganic nanoparticles ranging from ceramic-in-polymer to polymer-in-ceramic concentration regimes. First, a brief discussion on fundamental aspects of mixed ionic-electronic transport phenomena considering the charge carrier transport at bulk regions together with the effect of the organic-inorganic interphase of hybrid nanocomposites is presented. We also make a recount of updated instrumentation techniques to characterize structure, microstructure, chemical composition, and mixed ionic-electronic transport with special focus on those relevant for hOI-MIECs. Raman imaging and impedance spectroscopy instrumentation techniques are particularly discussed as relatively simple and versatile tools to study the charge carrier localization and transport at different regions of hOI-MIECs including both bulk and interphase regions to shed some light on the mixed ionic-electronic transport mechanism. In addition, we will also refer to different device assembly configurations and in situ/operando measurements experiments to analyze mixed ionic-electronic conduction phenomena for different specific applications. Finally, we will also review the broad range of promising applications of hOI-MIECs, mainly in the field of energy storage and conversion, but also in the emerging field of electronics and bioelectronics.

Extremely Large Magnetic-Field-Effects on the Impedance Response of TiO2 Quantum Dots.

Here, we report large magnetoresistance and magnetocapacitance response of undoped TiO2 quantum dots weighting the contribution of both grain and grain boundaries by means of impedance spectroscopy. We also performed a complete characterization of the TiO2 quantum dots (~5 nm) prepared by sol-gel via water vapor diffusion method, using X-ray diffraction, small angle X-ray scattering, transmission electron microscopy and Raman spectroscopy. In addition, we showed a complete theoretical study on the electronic properties of TiO2 surface and subsurface oxygen and titanium vacancies to shed some light in their electronic and magnetic properties. Based in our study, we can conclude that the presence of defects, mainly at the grain boundary of these undoped TiO2 quantum dots, could be responsible for the large positive magnetoresistance (+1200%) and negative magnetocapacitance (-115%) responses at low applied magnetic fields (1.8 kOe) and room temperature.

Physico-chemical and antilisterial properties of nisin-incorporated chitosan/carboxymethyl chitosan films.

The objective of this work was to investigate the effect of the addition of carboxymethyl chitosan on the structural properties and antilisterial activity of nisin-incorporated chitosan films. Chitosan and carboxymethyl chitosan solutions were prepared with different mass ratios and bacteriocin nisin was added (0, 1000 and 6000 IU/ml). Filmogenic solutions were cast, dried and their physico-chemical and antimicrobial properties were investigated. For the same chitosan/carboxymethyl chitosan mass ratio, the addition of NIS at 6000 IU/ml led to changes in the macro- and microstructure, as well as in physico-chemical properties of films. On the other hand, carboxymethyl chitosan had a plasticizing effect and enhanced the distribution of the bacteriocin within the biopolymer matrix. Moreover, nisin-incorporated blend films of chitosan and carboxymethyl chitosan were more effective against Listeria monocytogenes than their pure chitosan counterparts. This study showed that different formulations of nisin-incorporated composite films of chitosan and carboxymethyl chitosan may provide options for developing bioactive packaging to improve food safety.

Raman Microscopy Insights on the Out-of-Plane Electrical Transport of Carbon Nanotube-Doped PEDOT:PSS Electrodes for Solar Cell Applications.

In the present report, we focused on the study of the out-of-plane electrical transport of multiwalled carbon nanotube (MWCNT)-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composites (PEDOT:PSS-MWCNTs) as electrodes for solar cell applications. The out-of-plane direct current and alternating current electrical transport, rarely studied but not less relevant, was additionally supported with in-plane and out-of-plane confocal Raman microscopy and grazing incidence small-angle X-ray scattering characterizations. The main relevance of our study is the monitoring of the polymer structure all across the polymeric film by using confocal Raman spectroscopy and its correlation with electrical transport. Modifications in the PEDOT benzenoid and quinoid conformations were observed in the vicinities of MWCNTs, and the enrichment of PSS at the indium tin oxide electrode interface was also evidenced. In consequence, the low MWCNT loadings into PEDOT:PSS lead to an increase of the out-of-plane conductivity, but the heavier MWCNT loadings lead to a drastic decrease. The tuning of the doping level of these polymer composites and the understanding of the interface structure are crucial to fabricate electrodes with higher out-of-plane conductivities for organic solar cell applications.