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Soft Plasmomechanical Metamaterials for Sensing and Actuation Pau

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Soft Plasmomechanical Metamaterials for Sensing and Actuation Pau ADVERTIMENT. Lʼaccés als continguts dʼaquesta tesi queda condicionat a lʼacceptació de les condicions dʼús establertes per la següent llicència Creative Commons: http://cat.creativecommons.org/?page_id=184 ADVERTENCIA. El acceso a los contenidos de esta tesis queda condicionado a la aceptación de las condiciones de uso establecidas por la siguiente licencia Creative Commons: http://es.creativecommons.org/blog/licencias/ WARNING. The access to the contents of this doctoral thesis it is limited to the acceptance of the use conditions set by the following Creative Commons license: https://creativecommons.org/licenses/?lang=en Soft Plasmomechanical Metamaterials for Sensing and Actuation Pau Güell Grau Directors: Dra. Mar Álvarez Dr. Borja Sepúlveda Tutor: Dra. Eva Pellicer Universitat Autònoma de Barcelona Departament de Física Programa de Doctorat en Ciència de Materials Bellaterra (Barcelona), novembre 2020 The present work entitled “Soft plasmomechanical metamaterials for sensing and actuation”, presented by Pau Güell i Grau to obtain the degree of Doctor in Materials Science by Universitat Autònoma de Barcelona, was performed at the Biomedical Applications Group at the Instituto de Microelectrónica de Barcelona (IMB-CNM) and the Magnetic Nanostructures Group at the Institut Català de Nanociència i Nanotecnologia (ICN2), under the supervision of Dra. Mar Álvarez and Dr. Borja Sepúlveda. The present thesis was also performed under the doctoral program studies “Doctorat en Ciència de Materials” at the Physics Department, Science Faculty, Universitat Autònoma de Barcelona, under the tutorship of Dra. Eva Pellicer. Pau Güell i Grau (Author) Dra. Mar Alvarez Dr. Borja Sepúlveda Dra. Eva Pellicer (Director) (Director) (Tutor) PREFACE I. Acknowledgments Primer de tot vull agrair a els meus directors de tesi, Mar i Borja, per tota la feina feta durant aquests anys, per estar sempre disponibles a resoldre’m dubtes, ajudar-me amb els experiments, discussions científiques, etc. i sobretot pel bon tracte que sempre m’heu donat. Heu sabut complementar-vos a la perfecció per guiar-me durant aquests anys. També vull agrair als caps de grup, Rosa i Josep, per haver fet possible que hagi pogut treballar sota el paraigües del GAB i del MNG, respectivament. Del Grup d’Aplicacions Biomèdiques guardaré un especial record de tots amb els qui he pogut compartir part d’aquest temps: de l’Edu: nano original com jo, amic, company de pis, de despatx i més...; del Jose i el seu peculiar humor, de l’Ana i el seu caràcter, del Miguel Zea i el seu carisma, del meu company de línia Fernando... i del Xavi, Anton, Eli, Gemma, Javi, Daniel, Ferran, Miguel Aller, Javier del Campo... en resum, de tots els GABianos. Del Magnetic Nanostructures Group tres quarts del mateix, amb especials mencions pel Javi Muro, amb qui hem passat molts bons i mals moments al despatx, però sempre amb molt d’optimisme i humor absurd. I pel Li, sempre amb una bona paraula i obert a ajudar-te amb el que sigui. I a la resta de companys amb qui he tingut el plaer de coincidir: Yue, Guba, Nour, Filippos, Alex, Elvira, Patxi i Mª José. I no sent del grup, però que ha estat també molt present, Jose Fran, gràcies pel bon rotllo i les converses entre coffee breaks que hem tingut. També crec que és bon moment per recordar-me’n dels anys previs al doctorat, els companys nanos amb qui he compartit els 4 anys de carrera i que alguns s’han convertit o es convertiran també en doctors. Especialment per l’Arnau i l’Àlex, els qui he vist defensar les seves tesis i ara jo segueixo el mateix camí. I deixo pel final (però no per això menys importants) els meus agraïments per a la gent fora de l’àmbit acadèmic. Primer de tot, gràcies als meus pares per sempre recolzar-me amb els meus estudis i per creure cegament en mi. També a la resta de família per estar sempre acompanyant-me. I al Pep, que espero que li agradi llegir-se aquesta tesi. Finalment, no puc tancar els agraïments sense recordar-me’n de les persones amb qui he conviscut durant aquests últims 4 anys, les quals m’han vist passar-les de tots colors. En especial a la Zipotilla i a la Bananita, que m’han sofert de primeríssima mà, i amb poc temps s’han convertit en la meva segona família. També un record especial a la meva colla gironina, que finalment em podran dir “Dr. Güell” amb totes les de la llei; i als meus companys rugbiers, tant als Centaures com al BUC, que tot i que estic segur que molts encara no entenen a què em dedico, han sigut vitals per evadir-me en moments d’estrès. Amb aquesta tesi es tanca una etapa i inevitablement en començarà una altra, la qual no sé on em portarà, però que afronto amb moltes ganes i il·lusió per endavant. Pau Güell i Grau II. Resum Durant l’última dècada, els materials intel·ligents han emergit com a una tendència fascinant en la ciència de materials. El seu concepte principal consisteix en l’auto-resposta reversible a estimulació externa (com per exemple temperatura, llum o camps elèctrics) produint un canvi en les seves pròpies propietats fisicoquímiques (p. ex. forma, color o rigidesa), i es basen normalment en materials tous en combinació amb altres materials amb funcionalitats extra. En aquest àmbit, els materials optomecànics tous són especialment interessants per desenvolupar dispositius de sensat i actuació innovadors gràcies a la naturalesa inalàmbrica dels sistemes òptics, la selectivitat sintonitzable a diferents longituds d’ona i la possibilitat de ser combinada amb altres tipus d’estimulació (p. ex. camps elèctrics o magnètics). En particular, la inclusió de nanopartícules o nanoestructures plasmòniques en substrats polimèrics tous (p. ex. elastòmers) comporta possibilitats interessants, com les característiques òptiques fàcils de modificar dels materials plasmonics i la gran elasticitat i robustesa dels materials tous. Aquesta nova classe de materials és referida en aquesta tesi com a metamaterials plasmomecànics tous. Tot i així, aquest particular camp d’estudi es relativament recent, pel qual encara hi ha moltes oportunitats i reptes que han de ser afrontats. Per aquest motiu, aquesta tesi està dedicada al desenvolupament de nous metamaterials plasmomecànics tous, portant a terme l’estudi detallat de les seves propietats òptiques i mecàniques (englobant les ressonàncies plasmòniques, fenòmens fotònics i les respostes a esforç mecànic) i el seu disseny per a l’ús en aplicacions pràctiques en l’àmbit del sensat i l’actuació. La litografia col·loïdal és utilitzada per fabricar nanoestructures plasmòniques (Fe, Au), en combinació amb materials elastomèrics com el poli(dimetilsiloxà) (PDMS), per aconseguir cada particular metamaterial plasmomecànic. Específicament, les dificultats d’implementar absorbents de llum en ampla de banda eficients en substrats flexibles o elàstics són abordades amb el desenvolupament d’un nou metamaterial basat en una capa de ferro nanoestructurat sobre una capa fina elastomèrica. Aquest nou metamaterial combina les ressonàncies plasmòniques amortides del ferro nanoestructurat amb l’absorció infraroja del PDMS per aconseguir una absorció independent de l’angle i amb un ample de banda sense precedents (mitjana del 84% des de 300 a 18000 nm). Aquest excepcional comportament òptic, juntament amb un gran desajustament de les propietats mecàniques d’ambdós materials és explotat per a desenvolupar diversos dispositius foto-termo-mecànics inalàmbrics i innovadors. Específicament, un iris artificial autoregulat, biomimètic i sense alimentació s’ha desenvolupat, el qual modula la seva obertura interna en resposta a la intensitat de llum incident, i per tant auto-regulant la potència de llum transmesa. A més a més, una pinça controlada per llum i un interruptor elèctric activat via llum s’han desenvolupat per a demostrar la extensa aplicabilitat d’aquest metamaterial. La quasi-plana absorció en gran ample de banda permet l’actuació d’aquests dispositius mitjançant tant llum monocromàtica com policromàtica (làser, LED blanc o llum solar), i inclús la feble emissió infraroja d’emissors tèrmics. A més a més, la independència a l’angle d’incidència de la 10 Resum llum permet la efectivitat d’aquests dispositius en qualsevol orientació respecte a la llum incident. A través de l’explotació de les propietats magnètiques del ferro, el mateix metamaterial és utilitzat també per a desenvolupar un actuador inalàmbric i multi-funcional (responsiu tant òptica com magnèticament). Específicament, el control senzill de la força i direcció de l’actuació magnètica és combinada amb la actuació lumínica de gran ample de banda, permetent condicions d’operació remotes i versàtils per a aplicacions en robòtica tova. A més a més, s’ha aconseguit la incorporació de la funcionalitat d’auto-sensat a través d’incloure una estructura de reixa fotònica a la part posterior de l’actuador, la qual proveeix de coloració estructural a l’actuador. La resposta mecànica de l’actuador a qualsevol estímul extern (p. ex. òptic o magnètic) es mostra com a un canvi de coloració (resposta mecanocròmica) i és quantificada en temps real a través de l’anàlisi del valor Hue dels píxels de les imatges preses a través d’una càmera RGB convencional o d’un smartphone. L’actuació remota i multi-estímul del dispositiu, juntament amb les seves capacitats d’auto- sensat estableixen les bases per al desenvolupament de mecanismes en bucle per a sistemes inalàmbrics automatitzats, els quals són de gran interès per a operacions en robòtica tova en ambients inaccessibles o perillosos. Finalment, s’ha demostrat el desenvolupament de la primera cavitat Fabry-Perot estirable i amplificada plasmònicament, juntament amb la seva aplicabilitat per a sensat òptic d’esforç. Aquest nou material consisteix en una matriu de “mitja-closques” d’or plasmonic auto-organitzats, les quals són auto-incrustades dins un substrat elastomèric arrugat.
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