The research focuses on the development of new synthetic routes for the preparation of printable organic semiconductors, devised to be suitable for industrial scaling up. As such, a novel synthetic method for facile, cheap, and environmentally friendly production of π-extended organic semiconductors is explored. The concept sustainability is becoming a very important issue for chemical industries which are approaching green chemistry to reduce the environmental impact of chemical processes. In this frame, micellar catalysis has been demonstrated to be profitably performed in water under very mild conditions in the presence of a bit surfactant. Firstly, a self-emulsifying system L-α-Lecithin-Tween 80 mixture (TL82) is explored for the preparation of organic small molecules. The unique characteristic of this surfactant’s mixture offers a new environment for carrying out common cross coupling reactions such as Suzuki-Miyaura, Sonogashira and Heck cross-couplings in a reproducible up-scale way. The versatility of this approach is verified through the synthesis of complex organic semiconductors such as π-extended insoluble pigments. The emphasis on sustainability is not only applied to the synthesis but also to the processing of the active materials into the final target devices. Indeed, an innovative process is introduced enabling the preparation of high-performance thin film devices starting from waterborne dispersions of p- and n-type organic semiconductors. The TL82 self-emulsifying surfactant’s mixture is used both as the synthesis and processing medium. This method allows the preparation of Organic Field Effect Transistor using exclusively water in all steps with performances comparable to those synthesized and processed using common organic solvents. From the standpoint of the design of innovative materials, additional guidelines beside those aiming at achieving high performances are introduced. Original small molecules and polymers are designed selecting low-cost raw materials, severely the limiting the use of toxic and hazardous chemicals and designing all processes with up-scaling already in mind. These materials find an application in the field of (opto)electronics. An example of a good compromise between a simple design-good performance of a class of materials was investigated. In detail, a good part of the work was dedicated to the technology of luminescent solar concentrators devices, where the performances of the newly designed intrinsically sustainable materials are compared with those commercially available luminophores having similar spectral features. In the overall, we demonstrate comparable performance, but greatly improved sustainability and scalability. The final project was dedicated to the presentation of the first example of D-A regioregular polythiophene with an ambipolar character.

Il progetto di ricerca si concentra sullo sviluppo di nuove strategie sintetiche per la preparazione di semiconduttori organici stampabili e scalabili industrialmente. A tal fine, è stato introdotto un nuovo metodo sintetico per una facile, economica ed eco-sostenibile produzione di semiconduttori organici coniugati. Oggigiorno, il concetto di sostenibilità è una questione molto importante per le aziende che si impegnano nel rispettare i principi della Green Chemistry al fine di ridurre l'impatto ambientale dei processi chimici. In questo quadro, la catalisi micellare si è dimostrata un'ottima soluzione permettendo di condurre le reazioni utilizzando l’acqua come l’unico mezzo di reazione generalmente in presenza di piccoli quantitativi di surfattante. Ma purtroppo non sempre la catalisi micellare risulta essere riproducibile e facilmente scalabile industrialmente. A tal proposito, è stato studiato un sistema auto-emulsionante composto da una miscela di L-α-Lecitina e Tween 80 (TL82) per la preparazione di piccole molecole organiche. La caratteristica unica di questa miscela di tensioattivi offre un nuovo ambiente per l'esecuzione di comuni reazioni di cross-coupling come le reazioni di Suzuki-Miyaura, Sonogashira e Heck in modo riproducibile su larga scala. La versatilità di questo approccio è stata verificata attraverso la sintesi di semiconduttori organici complessi basati su pigmenti insolubili. La grande attenzione all'introduzione della sostenibilità non riguarda solo la sintesi, ma anche il processing dei materiali per la produzione di dispositivi. È stato introdotto un processo innovativo che consente la preparazione di dispositivi a film sottile ad alte prestazioni a partire da dispersioni acquose di semiconduttori organici sia di tipo p- che n-. La miscela di tensioattivi auto-emulsionante TL82 viene utilizzata sia come mezzo di sintesi che di processing. Questo metodo consente la preparazione di Transistor Organici ad Effetto di Campo utilizzando esclusivamente l’acqua in tutte le fasi di preparazione, ottenendo prestazioni paragonabili ai dispositivi ottenuti dai processi svolti utilizzando solventi organici. Sono stati inoltre progettati nuovi materiali innovativi performanti per l'(opto)elettronica. In particolari sono stati progettati sia piccole molecole che polimeri coniugati originali ponendo una grande attenzione al selezionamento di materie prime a basso costo, limitando severamente l'utilizzo di sostanze chimiche tossiche e pericolose e progettando tutti i processi per un possibile up-scaling. In dettaglio, buona parte del lavoro è stata dedicata allo sviluppo di materiali sostenibili per applicazione in concentratori solari luminescenti. Le prestazioni dei materiali sintetizzati sono state confrontate con quelle dei lumofori commercialmente disponibili con caratteristiche spettrali simili. Nel complesso, i nuovi materiali sviluppati mostrano prestazioni comparabili, ma col vantaggio di essere sintetizzati in maniera green e facilmente scalabili industrialmente. Infine, è stato sviluppato un monomero derivato tiofenico asimmetrico con caratteristiche intrinseche di donatore e accettore al fine di sviluppare uno dei primi esempi di polimero regio-regolare ambipolare.

(2022). Organic Materials for (Opto)electronics introducing Sustainability in Design, Synthesis and Manufacturing. (Tesi di dottorato, Università degli Studi di Milano-Bicocca, 2022).

Organic Materials for (Opto)electronics introducing Sustainability in Design, Synthesis and Manufacturing

CERIANI, CHIARA
2022

Abstract

The research focuses on the development of new synthetic routes for the preparation of printable organic semiconductors, devised to be suitable for industrial scaling up. As such, a novel synthetic method for facile, cheap, and environmentally friendly production of π-extended organic semiconductors is explored. The concept sustainability is becoming a very important issue for chemical industries which are approaching green chemistry to reduce the environmental impact of chemical processes. In this frame, micellar catalysis has been demonstrated to be profitably performed in water under very mild conditions in the presence of a bit surfactant. Firstly, a self-emulsifying system L-α-Lecithin-Tween 80 mixture (TL82) is explored for the preparation of organic small molecules. The unique characteristic of this surfactant’s mixture offers a new environment for carrying out common cross coupling reactions such as Suzuki-Miyaura, Sonogashira and Heck cross-couplings in a reproducible up-scale way. The versatility of this approach is verified through the synthesis of complex organic semiconductors such as π-extended insoluble pigments. The emphasis on sustainability is not only applied to the synthesis but also to the processing of the active materials into the final target devices. Indeed, an innovative process is introduced enabling the preparation of high-performance thin film devices starting from waterborne dispersions of p- and n-type organic semiconductors. The TL82 self-emulsifying surfactant’s mixture is used both as the synthesis and processing medium. This method allows the preparation of Organic Field Effect Transistor using exclusively water in all steps with performances comparable to those synthesized and processed using common organic solvents. From the standpoint of the design of innovative materials, additional guidelines beside those aiming at achieving high performances are introduced. Original small molecules and polymers are designed selecting low-cost raw materials, severely the limiting the use of toxic and hazardous chemicals and designing all processes with up-scaling already in mind. These materials find an application in the field of (opto)electronics. An example of a good compromise between a simple design-good performance of a class of materials was investigated. In detail, a good part of the work was dedicated to the technology of luminescent solar concentrators devices, where the performances of the newly designed intrinsically sustainable materials are compared with those commercially available luminophores having similar spectral features. In the overall, we demonstrate comparable performance, but greatly improved sustainability and scalability. The final project was dedicated to the presentation of the first example of D-A regioregular polythiophene with an ambipolar character.
BEVERINA, LUCA
Chimica verde; Catalisi Micellare; Sostenibilità; Cross-Coupling; Chimica Organica
Green Chemistry; Micellar Catalysis; Sustainability; Suzuki-Miyaura; Chimica Organica
CHIM/06 - CHIMICA ORGANICA
English
13-apr-2022
SCIENZA E NANOTECNOLOGIA DEI MATERIALI
34
2020/2021
embargoed_20250413
(2022). Organic Materials for (Opto)electronics introducing Sustainability in Design, Synthesis and Manufacturing. (Tesi di dottorato, Università degli Studi di Milano-Bicocca, 2022).
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/369035
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