Nanoestructurado de materia condensada blanda con aplicaciones en electrónica orgánica

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Físicas, leída el 21-10-2019Organic, light, flexible materials with functional properties as electrical conductivity and ferroelectricity that can be used in electronic devices are likely to be a safe bet for the future. However, these materials present much lower efficiencies compared with their analog inorganic materials. Therefore, a lot of research is still to be done to put organic materials in the competitive market. Nanostructuring is one of the most important approaches to achieve this objective, due in part to the requirement of miniaturization of electronic devices and because of the possibility of tuning the properties of these materials by modifying their structure at the nanoscale. This Thesis is focused on the fabrication of nanostructures on soft matter, mainly polymeric materials, with semiconducting and/or ferroelectric properties. Three kinds of nanostructures were fabricated: nanolayers or thin films (Chapter 3), surface nanostructures generated by laser irradiation (Chapter 4) and by nanoimprint lithography (Chapter 5), and nanoparticles (Chapter 6)...Los materiales orgánicos que presentan propiedades funcionales como la conductividad eléctrica y la ferroelectricidad, además de sus propiedades de ligereza y flexibilidad, son una apuesta segura para el futuro debido a la posibilidad de emplearlos en dispositivos electrónicos. Sin embargo, comparados con materiales inorgánicos análogos, presentan eficiencias mucho menores. Es por ello que aún debe realizarse un esfuerzo de investigación y desarrollo considerable, con el objetivo de colocar a estos materiales orgánicos en un nivel competitivo en el mercado. La nanoestructuración es uno de los caminos más investigados para conseguir este objetivo, no solo por la demanda actual de miniaturización de dispositivos electrónicos sino también por la posibilidad de modificar las propiedades funcionales de estos materiales mediante la alteración de su nanoestructura. Esta Tesis está enfocada a la fabricación y al estudio de nanoestructuras de materia condensada blanda, principalmente polímeros, con propiedades semiconductoras y/o ferroeléctricas. Se han fabricado tres tipos de nanoestructuras: nanocapas o películas delgadas (Capítulo 3), nanoestructuras superficiales mediante irradiación con láser (Capítulo 4) y nanoestructuras mediante litografía de nanoimpresión (Capítulo 5), así como nanopartículas (Capítulo 6).Fac. de Ciencias FísicasTRUEunpu

Preparation, Physical Properties, and Applications of Water-Based Functional Polymer Inks

In this study, water-based functional polymer inks are prepared using different solvent displacement methods, in particular, polymer functional inks based on semiconducting polymer poly(3-hexylthiophene) and the ferroelectric polymer poly(vinylidene fluoride) and its copolymers with trifluoroethylene. The nanoparticles that are included in the inks are prepared by miniemulsion, as well as flash and dialysis nanoprecipitation techniques and we discuss the properties of the inks obtained by each technique. Finally, an example of the functionality of a semiconducting/ferroelectric polymer coating prepared from water-based inks is presented.This research was funded by the Ministry of Science, grant number PID2019-107514GB-I00 and the National Natural Science Foundation of China (no. 51903224)

Y6 Organic Thin-Film Transistors with Electron Mobilities of 2.4 cm2 V−1 s−1 via Microstructural Tuning

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] There is a growing demand to attain organic materials with high electron mobility, μe, as current reliable reported values are significantly lower than those exhibited by their hole mobility counterparts. Here, it is shown that a well-known nonfullerene-acceptor commonly used in organic solar cells, that is, BTP-4F (aka Y6), enables solution-processed organic thin-film transistors (OTFT) with a μe as high as 2.4 cm2 V−1 s−1. This value is comparable to those of state-of-the-art n-type OTFTs, opening up a plethora of new possibilities for this class of materials in the field of organic electronics. Such efficient charge transport is linked to a readily achievable highly ordered crystalline phase, whose peculiar structural properties are thoroughly discussed. This work proves that structurally ordered nonfullerene acceptors can exhibit intrinsically high mobility and introduces a new approach in the quest of high μe organic materials, as well as new guidelines for future materials design.Ministerio de Ciencia e Innovación; PGC2018-094620-A-I00Xunta de Galicia; ED431F 2021/00

Influence of Backbone Curvature on the Organic Electrochemical Transistor Performance of Glycolated Donor–Acceptor Conjugated Polymers

[Abstract] Two new glycolated semiconducting polymers PgBT(F)2gT and PgBT(F)2gTT of differing backbone curvatures were designed and synthesised for application as p-type accumulation mode organic electrochemical transistor (OECT) materials. Both polymers demonstrated stable and reversible oxidation, accessible within the aqueous electrochemical window, to generate polaronic charge carriers. OECTs fabricated from PgBT(F)2gT featuring a curved backbone geometry attained a higher volumetric capacitance of 170 F cm−3. However, PgBT(F)2gTT with a linear backbone displayed overall superior OECT performance with a normalised peak transconductance of 3.00×104 mS cm−1, owing to its enhanced order, expediting the charge mobility to 0.931 cm2 V−1 s−1.Engineering and Physical Sciences Research Council; EP/T028513/1República de Corea. Ministry of Science, ICT and Future Planning; NRF-2017K1A1A2013153República de Corea. Ministry of Science, ICT and Future Planning; NRF-2021R1A2C1013015República de Corea. Ministry of Science, ICT and Future Planning; NRF-2018M3A7B4070988República de Corea. Ministry of Science, ICT and Future Planning; NRF-2020M3D1A1030660República de Corea. Ministry of Science, ICT and Future Planning; NRF-2020M1A2A208074

Sensado inalámbrico de gases en minería con servicio web en tiempo real

This paper presents the development and implementation of a wireless system and sensing of explosive gases in mining with web service in real time. The system consists of modules configured in a network of sensors arranged in the inner galleries of the mine; each one of these moduleshas the ability to receive signals from sensors of methane, carbon dioxide, the charge level of battery and an auxiliary sensor. This card has a module 900 Mhz Xbee pro DigiMesh, responsible for transmitting the sensor data. This data is sent to the external module which connects with a card Beaglebone that displays data on a web platform made in Python software, in which sensor data are stored in order to analyze the behavior of gases in time. The network is implemented in a tree topology configuring modules as routers and one as a coordinator that controls the network. The modules are organizedhierarchically in order to transmit the data to the entrance of the mine. Finally, the network configuration is done until the system enters in mode sleep (idle) when it is not receiving information, in this way the consuming power decreased, increasing the autonomy of the batteries. This paper describes the design, implementation and operation of a gas monitoring system in mining with web service inreal-time based on a network of Zigbee sensors.En este trabajo se plasma el desarrollo e implementación de un  sistema inalámbrico  y sensado de gases explosivos en minería con servicio web en tiempo real, el sistema está compuesto por módulos configurados en una red de sensores dispuestos en las galerías internas de la mina, cada uno estos módulos está en la capacidad de recibir señales provenientes de sensores de metano, dióxido de carbono, nivel de carga de las batería y un sensor auxiliar, cuenta con un módulo Xbee-pro 900 DigiMesh  encargado de la transmisión de los datos que entregan los sensores, estos datos se envían hacia el módulo más externo el cual conecta con una  tarjeta de desarrollo Beaglebone encargada de la visualización de los datos en una plataforma web realizada en software Python, en la cual se almacenan los datos  de los sensores con el fin de analizar el comportamiento de los gases en el tiempo. La red se implementa en una topología  árbol configurando los módulos  como routers y uno como coordinador encargado del control de la red. Los módulos se organizan de  manera jerárquica  con el fin  de transmitir los datos hacia la entrada de la mina, finalmente se realiza la configuración de la red para que el sistema entre en modo  sleep (inactividad) cuando no se está recibiendo información,  de esta forma se aumenta  la autonomía de la baterías que alimentan  a cada uno de los módulos. En este documento se muestra el diseño,  implementación  y  puesta en funcionamiento de un sistema de monitoreo  de gases en minería  con servicio web en tiempo real basado en una red de sensores Zigbee.

P-type Semiconducting Polymers as Photocathodes: A Comparative Study for Optobioelectronics

Recent studies have shown that p-type polymeric semiconductors enable a new type of wireless, optically triggered interface with cells and tissues. Poly(3-hexylthiophene-2,5-diyl) (P3HT) has already been used to create such optobioelectronic interfaces, producing reactive oxygen species and hydrogen peroxide that act as messengers in biological systems to impact cell signaling and proliferation. However, the use of P3HT in biomedical in-vivo applications is limited as its optical absorption does not match the tissue transparency window. This paper compares the performance of P3HT with two low band-gap polymers commonly employed in high-performance organic solar cells, namely Poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-1,3-diyl]] (PBDB-T) and Poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b] thiophenediyl}) (PTB7). Their photogeneration capabilities are quantified in physiological-like conditions through photocurrent analysis and a hydrogen peroxide assay, finding a superior photocurrent generation and a better H2O2 photogeneration yield in PTB7 as compared to the other two polymers. Spectroscopic and structural investigations are used to compare such differences by comparing their energy levels at the electrochemical interface and their morphologies. Finally, biocompatibility is tested both in dark and illuminated conditions and effective in-vitro intracellular ROS production is demonstrated. These findings provide insight into the physico-chemical properties crucial for the development of novel, less invasive, optically operated bioelectronic interfaces

Gold(III) Porphyrin Was Used as an Electron Acceptor for Efficient Organic Solar Cells

[Abstract] The widespread use of nonfullerene-based electron-accepting materials has triggered a rapid increase in the performance of organic photovoltaic devices. However, the number of efficient acceptor compounds available is rather limited, which hinders the discovery of new, high-performing donor:acceptor combinations. Here, we present a new, efficient electron-accepting compound based on a hitherto unexplored family of well-known molecules: gold porphyrins. The electronic properties of our electron-accepting gold porphyrin, named VC10, were studied by UV−Vis spectroscopy and by cyclic voltammetry (CV) , revealing two intense optical absorption bands at 500−600 and 700−920 nm and an optical bandgap of 1.39 eV. Blending VC10 with PTB7-Th, a donor polymer, which gives rise to an absorption band at 550−780 nm complementary to that of VC10, enables the fabrication of organic solar cells (OSCs) featuring a power conversion efficiency of 9.24% and an energy loss of 0.52 eV. Hence, this work establishes a new approach in the search for efficient acceptor molecules for solar cells and new guidelines for future photovoltaic material designF.L. and P.d.l.C. thank MCI (Spain) (PID2019-105049RB-I00), MICIU (RED2018-102815-T), the Junta de Comunidades de Castilla-La Mancha, and the European Social Fund (SBPLY/17/180501/000254) for financial support. V.C. thanks MECD for an FPU grant (FPU15/02170). G.D.S. thanks the Government of India SERI-DST (DST/TMD/SERI/D05(c)) for financial support. J.M. thanks the MICINN for grant PGC2018-094620-A-I00Junta de Comunidades de Castilla-La Mancha; SBPLY/17/180501/000254Government of India; DST/TMD/SERI/D05(c

Gold(III) Porphyrin Was Used as an Electron Acceptor for Efficient Organic Solar Cells

[EN] The widespread use of nonfullerene-based electron-accepting materials has triggered a rapid increase in the performance of organic photovoltaic devices. However, the number of efficient acceptor compounds available is rather limited, which hinders the discovery of new, high-performing donor:acceptor combinations. Here, we present a new, efficient electron-accepting compound based on a hitherto unexplored family of well-known molecules: gold porphyrins. The electronic properties of our electron-accepting gold porphyrin, named VC10, were studied by UV-Vis spectroscopy and by cyclic voltammetry (CV) , revealing two intense optical absorption bands at 500-600 and 700-920 nm and an optical bandgap of 1.39 eV. Blending VC10 with PTB7-Th, a donor polymer, which gives rise to an absorption band at 550-780 nm complementary to that of VC10, enables the fabrication of organic solar cells (OSCs) featuring a power conversion efficiency of 9.24% and an energy loss of 0.52 eV. Hence, this work establishes a new approach in the search for efficient acceptor molecules for solar cells and new guidelines for future photovoltaic material design.F.L. and P.d.l.C. thank MCI (Spain) (PID2019-105049RB-I00), MICIU (RED2018-102815-T), the Junta de Comunidades de Castilla-La Mancha, and the European Social Fund (SBPLY/17/180501/000254) for financial support. V.C. thanks MECD for an FPU grant (FPU15/02170). G.D.S. thanks the Government of India SERI-DST (DST/TMD/SERI/D05(c)) for financial support. J.M. thanks the MICINN for grant PGC2018-094620-A-I00

Stable and Solution-Processable Cumulenic sp-Carbon Wires: A New Paradigm for Organic Electronics

[EN] Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp(2)-hybridized carbon molecules, either in the form of pi-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm(2 )V(-1 )s(-1), as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.E.G.F. acknowledges the support through the EU Horizon 2020 research and innovation program, H2020-FETOPEN-01-2018-2020 (FET-Open Challenging Current Thinking), "LION-HEARTED", grant agreement no. 828984. C.S.C. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program ERC-Consolidator Grant (ERC CoG 2016 EspLORE grant agreement no. 724610, website: ). R.R.T. acknowledges funding from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI). This work was partially supported by the European Union's H2020-EU.4.b. - Twinning of research institutions "GREENELIT", grant agreement number 951747. GIWAXS experiments were performed at BL11 NCD-SWEET beamline at ALBA Synchrotron (Spain) with the collaboration of ALBA staff. This work was in part carried out at Polifab, the micro- and nanotechnology centre of the Politecnico di Milano. Open access funding provided by Istituto Italiano di Tecnologia within the CRUI-CARE Agreement