Gli autori riconoscono con gratitudine il sostegno finanziario da l'US Air Force Office of Scientific Research, sotto il numero di contratto FA9550-14-1-0128. T. L. A. ringrazia anche parziale supporto da David e Lucille Packard Foundation.

Leggere MSDS per reagenti e seguire tutte le misure di sicurezza chimica come richiesto dalla vostra istituzione.
1. deposizione di Cl-PProDOT e Cl-PTT
<ol><li>Costruire la struttura della camera di deposizione di vapore tubolari su misura come mostrato in Figura 1.<ol>
<li>Fare un 1/4-pollici (diametro esterno, O.D.) fusi quarzo ingresso laterale ad un tubo di quarzo fuso 2-pollici (diametro esterno). Fare una trappola a freddo con un tubo di acciaio inox di 1-in U-forma su misura e un pallone Dewar.</li>
		<li>Collegare il tubo di quarzo con un vacuometro e trappola a freddo utilizzando acciaio inossidabile KF connettori e innesti rapidi. Posizionare il monomero in una fiala di quarzo e collegare la fiala alla camera tubolare via 1/4-pollici rapido-attacchi rapidi e una valvola a spillo. Posto l'ossidante in un crogiolo in aula.</li>
		<li>Utilizzare nastri di riscaldamento separati come fonti per l'ossidante, substrati e il monomero di riscaldamento. Aggiungere un ingresso gas all'estremità destra della camera di introdurre ulteriori gas nobili per controllare la pressione di processo, se necessario.</li>
	</ol>
</li>
	<li>
Deposizione di Cl-PProDOT
	<ol>
<li>Aggiungere 50 mg di 3,4-propylenedioxythiophene (ProDOT) nella fiala monomero e collegarlo alla camera tubolare. Tenere aperta la valvola a spillo.</li>
		<li>Mettere substrati (lastra di vetro, tessuti, carta, ecc.) in aula. La dimensione dei substrati è 1,3 x 2,5 cm.</li>
		<li>Aggiungere 50 mg di FeCl3 in un crogiolo di 5 mL e posizionarlo nella camera. Nota: Le posizioni relative dell'ingresso di monomero, substrati e il crogiolo sono mostrate nella Figura 1. La distanza tra l'entrata di monomero e il crogiolo è 13 cm.</li>
		<li>Accendere la pompa. Chiudere lentamente la valvola all'estremità destra della camera. Dopo la camera di pressione è inferiore a mTorr 525 (70 Pa), aggiungere azoto liquido nella trappola fredda.</li>
		<li>Avvolgere le tre zone di riscaldamento con riscaldamento nastro e collegare il nastro di riscaldamento per i regolatori di temperatura.</li>
		<li>Quando la pressione diminuisce la pressione di lavorazione (52,5 mTorr, 7 Pa), chiudere la valvola a spillo del contenitore monomero.</li>
		<li>Iniziare il riscaldamento l'ossidante, i substrati e il monomero a 170 ° C, 80 ° C e 80 ° C, rispettivamente. Dopo circa 10 min, FeCl3 è vaporizzato e il rosso di FeCl3 solido è formata nella regione cool.</li>
		<li>Aprire la valvola a spillo del contenitore monomero. Nota: Film sottili di colore blu si formerà la regione di substrato. Tassi di crescita tipici sono ~ 10 nm/min affinché il FeCl3 vapor è formata nella camera prima di aprire la valvola a spillo del contenitore monomero. In caso contrario, il monomero reagisce con FeCl3 solido nel crogiolo e formare uno strato di polimero che previene l'ulteriore vaporizzazione di ossidante.</li>
		<li>Chiudere la valvola a spillo del contenitore monomero quando è raggiunto lo spessore desiderato. Spegnere tutto il nastro di riscaldamento e raffreddare il sistema a temperatura ambiente.</li>
		<li>Aprire la valvola di aspirazione di gas e spegnere la pompa.</li>
		<li>Prelevare i campioni dalla camera. Attentamente e immergere i campioni in metanolo per 30 min rimuovere il residuo dell'ossidante e monomero. Nota: Tempo di risciacquo dovrebbe aumentare come aumenti di spessore di pellicola. 30-min risciacquo è tipico per i film più sottile di 100 nm sulle lastre di vetro. Film più spessi di 500 nm potrebbe delaminare dal substrato durante il risciacquo.</li>
		<li>Colpo asciugare accuratamente i campioni con gas azoto.</li>
	</ol>
</li>
	<li>
Deposizione di Cl-PTT
	<ol>
<li>Aggiungere 50 mg di thieno [3,2 -b] tiofene (TT) nella fiala di monomero e collegarlo alla camera tubolare. Tenere aperta la valvola a spillo.</li>
		<li>Ripetere i passaggi 1.2.2. a 1.2.12.</li>
	</ol>
</li>
</ol>2. deposizione di Br-PEDOT
<ol><li>
Installazione di camera di deposizione
	<ol>
<li>Aggiungere un'ingresso laterali supplementari 1/4-pollici ossidanti per il tubo di quarzo e renderlo 8 pollici a parte l'ingresso di monomero. Posizionare l'ossidante liquido in una fiala di quarzo e collegare la fiala alla camera tubolare alla stessa stregua del monomero (Figura 2).</li>
	</ol>
</li>
	<li>
Deposizione di Br-PEDOT
	<ol>
<li>Aggiungere 2 mL di 3,4-ethylenedioxythiophene (EDOT) nella fiala di monomero e collegare la fiala alla camera tubolare. Tenere aperta la valvola a spillo.</li>
		<li>Posizionare substrati (lastra di vetro, tessuti, carta, ecc.) nell'alloggiamento tubolare vicino all'ingresso del vapore di monomero. La dimensione del substrato è 1,3 x 2,5 cm.</li>
		<li>In una cappa, aggiungere 2 mL di Br2 in fiala dell'ossidante, collegare la fiala per la valvola a spillo e mantenere la valvola a spillo chiusa. Collegare la valvola a spillo per il tubo di quarzo. Attenzione: BR2 è un materiale pericoloso. Prestare attenzione durante la manipolazione.</li>
		<li>Accendere la pompa. Chiudere lentamente la valvola all'estremità destra della camera. Dopo la camera di pressione è inferiore a mTorr 525 (70 Pa), aggiungere azoto liquido nella trappola fredda.</li>
		<li>Avvolgere la regione di monomero con riscaldamento nastro e collegarlo con un regolatore di temperatura. Mantenere il substrato e ossidante regione a temperatura ambiente.</li>
		<li>Quando la pressione diminuisce alla pressione di elaborazione di 52,5 mTorr (7 Pa), aprire la valvola a spillo di ossidante. Nota: La reazione è molto veloce. Blu film PEDOT formeranno vicino l'ingresso di monomero perché Br2 è molto volatile.</li>
		<li>Chiudere le valvole a spillo di entrambi il monomero e l'ossidante quando è raggiunto lo spessore desiderato.</li>
		<li>Spegnere il riscaldamento nastro e raffreddare il sistema a temperatura ambiente.</li>
		<li>Aprire la valvola di aspirazione di gas e spegnere la pompa. Prelevare i campioni dalla camera. Nota: Risciacquo non è necessaria per Br2-drogato con polimeri.</li>
	</ol>
</li>
</ol>

<ol>
	<li>Kaltenbrunner, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultrathin+and+lightweight+organic+solar+cells+with+high+flexibility.">Ultrathin and lightweight organic solar cells with high flexibility.</a> Nat. Commun. 3, 770 (2012).</li><li>Savagatrup, S., Printz, A. D., O'Connor, T. F., Zaretski, A. V., Lipomi, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecularly+Stretchable+Electronics.">Molecularly Stretchable Electronics.</a> Chem. Mater. 26, 3028-3041 (2014).</li><li>Lee, J. -. Y., Connor, S. T., Cui, Y., Peumans, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Semitransparent+Organic+Photovoltaic+Cells+with+Laminated+Top+Electrode.">Semitransparent Organic Photovoltaic Cells with Laminated Top Electrode.</a> Nano Lett. 10, 1276-1279 (2010).</li><li>Kaltenbrunner, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+ultra-lightweight+design+for+imperceptible+plastic+electronics.">An ultra-lightweight design for imperceptible plastic electronics.</a> Nature. 499, 458-463 (2013).</li><li>Jost, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Carbon+coated+textiles+for+flexible+energy+storage.">Carbon coated textiles for flexible energy storage.</a> Energy Environ. Sci. 4, 5060-5067 (2011).</li><li>Hu, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stretchable,+Porous,+and+Conductive+Energy+Textiles.">Stretchable, Porous, and Conductive Energy Textiles.</a> Nano Lett. 10, 708-714 (2010).</li><li>Jost, K., Dion, G., Gogotsi, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Textile+energy+storage+in+perspective.">Textile energy storage in perspective.</a> J. Mater. Chem. A. 2, 10776-10787 (2014).</li><li>Ding, Y., Invernale, M. A., Sotzing, G. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conductivity+Trends+of+PEDOT-PSS+Impregnated+Fabric+and+the+Effect+of+Conductivity+on+Electrochromic+Textile.">Conductivity Trends of PEDOT-PSS Impregnated Fabric and the Effect of Conductivity on Electrochromic Textile.</a> ACS Appl. Mater. Interfaces. 2, 1588-1593 (2010).</li><li>Hong, K. H., Oh, K. W., Kang, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+and+properties+of+electrically+conducting+textiles+by+in+situ+polymerization+of+poly(3,4-ethylenedioxythiophene).">Preparation and properties of electrically conducting textiles by in situ polymerization of poly(3,4-ethylenedioxythiophene).</a> J. Appl. Polym. Sci. 97, 1326-1332 (2005).</li><li>Xu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabric+electrodes+coated+with+polypyrrole+nanorods+for+flexible+supercapacitor+application+prepared+via+a+reactive+self-degraded+template.">Fabric electrodes coated with polypyrrole nanorods for flexible supercapacitor application prepared via a reactive self-degraded template.</a> Org. Electron. 26, 292-299 (2015).</li><li>Du, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermoelectric+Fabrics:+Toward+Power+Generating+Clothing.">Thermoelectric Fabrics: Toward Power Generating Clothing.</a> Sci. Rep. 5, 6411 (2015).</li><li>Yatvin, J., Sherman, S. A., Filocamo, S. F., Locklin, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+functionalization+of+Kevlar[registered+sign]+with+copolymers+containing+sulfonyl+nitrenes.">Direct functionalization of Kevlar[registered sign] with copolymers containing sulfonyl nitrenes.</a> Polym. Chem. 6, 3090-3097 (2015).</li><li>Musumeci, C., Hutchison, J. A., Samori, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlling+the+morphology+of+conductive+PEDOT+by+in+situ+electropolymerization:+from+thin+films+to+nanowires+with+variable+electrical+properties.">Controlling the morphology of conductive PEDOT by in situ electropolymerization: from thin films to nanowires with variable electrical properties.</a> Nanoscale. 5, 7756-7761 (2013).</li><li>Allison, L., Hoxie, S., Andrew, T. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Towards+seamlessly-integrated+textile+electronics:+methods+to+coat+fabrics+and+fibers+with+conducting+polymers+for+electronic+applications.">Towards seamlessly-integrated textile electronics: methods to coat fabrics and fibers with conducting polymers for electronic applications.</a> Chem. Commun. 53, 7182-7193 (2017).</li><li>Alf, M. E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical+Vapor+Deposition+of+Conformal,+Functional,+and+Responsive+Polymer+Films.">Chemical Vapor Deposition of Conformal, Functional, and Responsive Polymer Films.</a> Adv. Mater. 22, 1993-2027 (2010).</li><li>Goktas, H., Wang, X., Boscher, N. D., Torosian, S., Gleason, K. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Functionalizable+and+electrically+conductive+thin+films+formed+by+oxidative+chemical+vapor+deposition+(oCVD)+from+mixtures+of+3-thiopheneethanol+(3TE)+and+ethylene+dioxythiophene+(EDOT).">Functionalizable and electrically conductive thin films formed by oxidative chemical vapor deposition (oCVD) from mixtures of 3-thiopheneethanol (3TE) and ethylene dioxythiophene (EDOT).</a> J. Mater. Chem. C. 4, 3403-3414 (2016).</li><li>Sadki, S., Schottland, P., Brodie, N., Sabouraud, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+mechanisms+of+pyrrole+electropolymerization.">The mechanisms of pyrrole electropolymerization.</a> Chem. Soc. Rev. 29, 283-293 (2000).</li><li>Bhattacharyya, D., Howden, R. M., Borrelli, D. C., Gleason, K. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vapor+phase+oxidative+synthesis+of+conjugated+polymers+and+applications.">Vapor phase oxidative synthesis of conjugated polymers and applications.</a> J. Polym. Sci., Part B: Polym. Phys. 50, 1329-1351 (2012).</li><li>Yamato, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+free-standing+poly(3,4-ethylenedioxythiophene)+conducting+polymer+films+on+a+pilot+scale.">Synthesis of free-standing poly(3,4-ethylenedioxythiophene) conducting polymer films on a pilot scale.</a> Synth. Met. 83, 125-130 (1996).</li><li>Cheng, N., Zhang, L., Joon Kim, J., Andrew, T. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vapor+phase+organic+chemistry+to+deposit+conjugated+polymer+films+on+arbitrary+substrates.">Vapor phase organic chemistry to deposit conjugated polymer films on arbitrary substrates.</a> J. Mater. Chem. C. 5, 5787-5796 (2017).</li><li>Borrelli, D. C., Lee, S., Gleason, K. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Optoelectronic+properties+of+polythiophene+thin+films+and+organic+TFTs+fabricated+by+oxidative+chemical+vapor+deposition.">Optoelectronic properties of polythiophene thin films and organic TFTs fabricated by oxidative chemical vapor deposition.</a> J. Mater. Chem. C. 2, 7223-7231 (2014).</li><li>Jo, W. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Oxidative+Chemical+Vapor+Deposition+of+Neutral+Hole+Transporting+Polymer+for+Enhanced+Solar+Cell+Efficiency+and+Lifetime.">Oxidative Chemical Vapor Deposition of Neutral Hole Transporting Polymer for Enhanced Solar Cell Efficiency and Lifetime.</a> Adv. Mater. 28, 6399-6404 (2016).</li><li>Wang, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CVD+Polymers+for+Devices+and+Device+Fabrication.">CVD Polymers for Devices and Device Fabrication.</a> Adv. Mater. 29, 1604606 (2017).</li><li>Kovacik, P., Hierro, G. d., Livernois, W., Gleason, K. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Scale-up+of+oCVD:+large-area+conductive+polymer+thin+films+for+next-generation+electronics.">Scale-up of oCVD: large-area conductive polymer thin films for next-generation electronics.</a> Mater. Horiz. 2, 221-227 (2015).</li><li>Barr, M. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+Monolithic+Integration+of+Organic+Photovoltaic+Circuits+on+Unmodified+Paper.">Direct Monolithic Integration of Organic Photovoltaic Circuits on Unmodified Paper.</a> Adv. Mater. 23, 3500-3505 (2011).</li></ol>

Gli autori non hanno nulla a rivelare.

Il meccanismo della reazione è polimerizzazione ossidativa. Metodi di rivestimento di polimero utilizzando lo stesso meccanismo includono elettropolimerizzazione17 e fase polimerizzazione18di vapore. Elettropolimerizzazione richiede un substrato conduttivo, manca il vantaggio del rivestimento uniforme e conformal ed è un metodo basato sulla soluzione ecologicamente scortese19. Il metodo di polimerizzazione di fase del vapore esistente è simile al ...

Conducendo polimerici e materiali semiconduttori hanno proprietà uniche, come flessibilità1, elasticità2, trasparenza3, bassa densità,4 che offrono straordinarie opportunità per la creazione di nuova generazione dispositivi elettronici su substrati non tradizionali. Attualmente, molti ricercatori si sforzano di sfruttare le proprietà uniche di materiali polimerici per creare flessibile e/o elettronica indossabile5,6 e smart textiles7. Tuttavia, la capacità di conformally rivestire superfici altamente strutturate e substrati non-robusto, come carta, tessuti e filati/filati, rimane unmastered. Più comunemente, i polimeri vengono sintetizzati e rivestiti su superfici utilizzando metodi di soluzione. 8 , 9 , 10 , 11 , 12 anche se i metodi di soluzione forniscono polimero rivestito fibre/tessuti, i rivestimenti così ottenuti sono spesso non uniforme e facilmente danneggiabili da piccole sollecitazioni fisiche13,14 . Metodi di soluzione non sono inoltre applicabili a carta di rivestimento a causa di problemi di bagnatura.
Deposizione di vapore reattiva può creare film polimerici coniugati conformal su una vasta gamma di substrati, indipendentemente dalla composizione chimica superficiale, energia superficiale e rugosità/topografia superficiale15. In questo approccio, polimeri coniugati sono sintetizzate in fase gassosa fornendo contemporaneamente monomero e ossidante vapori ad una superficie. Formazione di pellicola e polimerizzazione avviene sulla superficie in un passaggio unico, privo di solventi. Questo metodo è teoricamente applicabile a qualsiasi polimero coniugato che può essere sintetizzato dalla polimerizzazione ossidativa utilizzando metodi di soluzione. Tuttavia, ad oggi, sono noti protocolli per depositare solo una serie limitata di strutture polimeriche coniugati. 15
Qui, dimostriamo la deposizione di poly(3,4-ethylenedioxythiophene) conduttivo (PEDOT) e poly(3,4-propylenedioxythiophene) (PProDOT) e di semiconduttori poli (thieno [3,2 -b] tiofene) film (PTT) tramite deposizione di vapore reattiva. Vengono utilizzati due tipi di ossidanti, tinta FeCl3 e liquido Br2, nel processo. I polimeri corrispondenti sono denominati Cl-PProDOT, Cl-PTT e Br-PEDOT. Sia substrati convenzionali, vetrini e substrati strutturati non convenzionali, quali carta, asciugamani e tessuti, sono stati rivestiti con il film di polimero.
Questo protocollo descrive la configurazione della camera di deposizione di vapore su misura e i dettagli del processo di deposizione. È inteso per aiutare gli operatori nuovi per costruire il loro sistema di deposizione e di evitare problemi comuni associati con sintesi in fase vapore.

<table>
	<tbody>
		<tr>
			<td>3,4-Ethylenedioxythiophene, 97%</td>
			<td>Sigma Aldrich</td>
			<td>483028</td>
			<td></td>
		</tr>
		<tr>
			<td>3,4-Propylenedioxythiophene, 97%</td>
			<td>Sigma Aldrich</td>
			<td>660485</td>
			<td></td>
		</tr>
		<tr>
			<td>Thieno[3,2-b]thiophene, 95%</td>
			<td>Sigma Aldrich</td>
			<td>702668</td>
			<td></td>
		</tr>
		<tr>
			<td>FeCl3, 97%</td>
			<td>Sigma Aldrich</td>
			<td>157740</td>
			<td></td>
		</tr>
		<tr>
			<td>Br2</td>
			<td>Sigma Aldrich</td>
			<td>207888</td>
			<td></td>
		</tr>
	</tbody>
</table>

reactive vapor deposition of conjugated polymer films on arbitrary substrates

Dimostriamo un metodo di rivestimento conformally polimeri coniugati su substrati arbitrari utilizzando una camera di reazione personalizzati, a bassa pressione. Polimeri conduttivi, poly(3,4-ethylenedioxythiophene) (PEDOT) e poly(3,4-propylenedioxythiophene) (PProDOT) e un polimero semiconduttore, poli (thieno [3,2 -b] tiofene) (PTT), sono stati depositati il non convenzionale altamente disordinata e substrati martellate con elevate superfici, quali carta, asciugamani e tessuti. Questo segnalato camera di deposizione è un miglioramento dei precedenti reattori del vapore perché il nostro sistema può ospitare monomeri sia volatili e non volatili, quali 3,4-propylenedioxythiophene e thieno [3,2 -b] tiofene. L'utilizzo di solidi e liquidi ossidanti sono anche dimostrato. Una limitazione di questo metodo è che manca un sofisticato in situ spessore monitor. Rivestimenti polimerici realizzati con i metodi di rivestimento basato su soluzione comunemente utilizzato, come rivestimento per rotazione e superficie l'innesto, spesso non sono uniformi o suscettibile di degradazione meccanica. Questo segnalato metodo di deposizione di vapore fase supera questi inconvenienti ed è una valida alternativa ai comuni metodi di rivestimento a base di soluzione. In particolare, film polimerici rivestito dal metodo segnalato sono uniformi e conformal su superfici ruvide, anche a una scala micrometrica. Questa funzionalità consente per la futura applicazione di polimeri vapor depositato in dispositivi elettronici su substrati flessibili e altamente strutturati.

Lo spessore del film di Cl-PProDOT formati su vetrini di 1,3 x 2,5 cm, collocati in posizioni discrete laterale lungo il tubo centrale sono stati misurati da un profilometro (Figura 3). Conducibilità sono stati calcolati dalle misure di resistività utilizzando una stazione di prova casa costruita quattro punti sonda. La conducibilità misurata di un film di Cl-PProDOT 100-nm spesso sulle lastre di vetro è 106 S/cm, che è sufficiente per qualificare questo...

Watch this Scientific Journal Video about Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates at JoVE.com

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Deposizione di vapore reattiva di film polimerici coniugati su substrati arbitrari

Questa carta presenta un protocollo per la deposizione di vapore reattiva di poly(3,4-ethylenedioxythiophene), di poly(3,4-propylenedioxythiophene) e di poli (thieno [3,2 -b] tiofene) film su lastre di vetro e superfici ruvide, come tessuti e carta.

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. ...

reactive-vapor-deposition-conjugated-polymer-films-on-arbitrary

Research

JoVE Journal

Chemistry

33.5K Views.  University of Wisconsin-Madison. Questa carta presenta un protocollo per la deposizione di vapore reattiva di poly(3,4-ethylenedioxythiophene), di poly(3,4-propylenedioxythiophene) e di poli (thieno [3,2 -b] tiofene) film su lastre di vetro e superfici ruvide, come tessuti e carta.

Video: Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

Preparazione del idrofobi Frameworks Metal-Organic tramite Plasma avanzata Chemical Vapor Deposition del perfluoroalcani per la rimozione di ammoniaca

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

Ricerca

Chimica

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

Fabbricazione di ampia superficie Free-standing ultrasottili film polimerici

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at &#60;60 &#176;C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

We present the synthesis of the organic-based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x, x~2) via low temperature chemical vapor deposition (CVD). This optimized recipe yields an increase in Curie temperature from 400 K to over 600 K and a dramatic improvement in magnetic resonance properties.

Chemical Vapor Deposition di un magnete biologico, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in ...

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application.
Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients.
The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating.

In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

Sintesi layer-by-layer e di trasferimento delle Freestanding coniugati microporosi Polymer nanomembrane

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

Preparazione di macroporosi Epitassiali Films quarzo su silicio da Solution Chemical Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Capillary Electrophoresis to Monitor Peptide Grafting onto Chitosan Films in Real Time

Free-solution capillary electrophoresis (CE) separates analytes, generally charged compounds in solution through the application of an electric field. Compared to other analytical separation techniques, such as chromatography, CE is cheap, robust and effectively requires no sample preparation (for a number of complex natural matrices or polymeric samples). CE is fast and can be used to follow the evolution of mixtures in real time (e.g., chemical reaction kinetics), as the signals observed for the separated compounds are directly proportional to their quantity in solution.
Here, the efficiency of CE is demonstrated for monitoring the covalent grafting of peptides onto chitosan films for subsequent biomedical applications. Chitosan&#39;s antimicrobial and biocompatible properties make it an attractive material for biomedical applications such as cell growth substrates. Covalently grafting the peptide RGDS (arginine - glycine - aspartic acid - serine) onto the surface of chitosan films aims at improving cell attachment. Historically, chromatography and amino acid analysis have been used to provide a direct measurement of the amount of grafted peptide. However, the fast separation and absence of sample preparation provided by CE enables equally accurate yet real-time monitoring of the peptide grafting process. CE is able to separate and quantify the different components of the reaction mixture: the (non-grafted) peptide and the chemical coupling agents. In this way the use of CE results in improved films for downstream applications.
The chitosan films were characterized through solid-state NMR (nuclear magnetic resonance) spectroscopy. This technique is more time-consuming and cannot be applied in real time, but yields a direct measurement of the peptide and thus validates the CE technique.

Free solution capillary electrophoresis is a fast, cheap and robust analytical method that enables the quantitative monitoring of chemical reactions in real time. Its utility for rapid, convenient and precise analysis is demonstrated here through analysis of covalent peptide grafting onto chitosan films for improved cell adhesion.

Elettroforesi capillare per monitorare Peptide innesto su Chitosano film in tempo reale

Free-solution capillary electrophoresis (CE) separates analytes, generally charged compounds in solution through the application of an electric field. ...

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH3NH3I) and methylammonium bromide (CH3NH3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH3NH3PbX3 with X = I, Br, Cl and their mixture) films with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH3NH3PbI3-xBrx by exposing the substrate to vapors of a mixture of CH3NH3I and CH3NH3Br at reduced pressure and 120 &#176;C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH3NH3PbI3-xBrx with 0&#160;&#8804; x&#160;&#8804; 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV&#160;&#8804; Eg&#160;&#8804; 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH3NH3PbI3-xClx. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.

Here, we present a protocol for the synthesis of CH3NH3I and CH3NH3Br precursors and the subsequent formation of pinhole-free, continuous CH3NH3PbI3-xBrx thin films for the application in high efficiency solar cells and other optoelectronic devices.

Bassa pressione processo di soluzione Vapor-assistita per sintonizzabile Band Gap Pinhole Metilammonio piombo ad alogenuri Perovskite film

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, ...

Aerosol-assisted Chemical Vapor Deposition of Metal Oxide Structures: Zinc Oxide Rods

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, their high cost production and/or incompatibility with microfabrication technologies, due to the use of pre-deposited catalyst-seeds and/or high processing temperatures exceeding 900 &#176;C, represent a drawback for a widespread use of these methods. Here, however, we report the synthesis of ZnO rods via a non-catalyzed vapor-solid mechanism enabled by using an aerosol-assisted chemical vapor deposition (CVD) method at 400 &#176;C with zinc chloride (ZnCl2) as the precursor and ethanol as the carrier solvent. This method provides both single-step formation of ZnO rods and the possibility of their direct integration with various substrate types, including silicon, silicon-based micromachined platforms, quartz, or high heat resistant polymers. This potentially facilitates the use of this method at a large-scale, due to its compatibility with state-of-the-art microfabrication processes for device manufacture. This report also describes the properties of these structures (e.g., morphology, crystalline phase, optical band gap, chemical composition, electrical resistance) and validates its gas sensing functionality towards carbon monoxide.

Columnar zinc oxide structures in the form of rods are synthesized via aerosol-assisted chemical vapor deposition without the use of pre-deposited catalyst-seed particles. This method is scalable and compatible with various substrates based on either silicon, quartz or polymers.

Aerosol-assisted Chemical Vapor Deposition di strutture in ossido di metallo: aste di ossido di zinco

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, ...

Monitoring the Effects of Illumination on the Structure of Conjugated Polymer Gels Using Neutron Scattering

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and absence of white light exposure. By instituting a controlled temperature ramp, the gelation of these materials can be precisely monitored as they proceed through this structural evolution, which effectively mirrors the conditions experienced during the solution deposition phase of organic electronic device fabrication. Using small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) along with appropriate fitting protocols we quantify the evolution of select structural parameters throughout this process. Thorough analysis indicates that continued light exposure throughout the gelation process significantly alters the structure of the ultimately formed gel. Specifically, the aggregation process of poly(3-hexylthiophene-2,5-diyl) (P3HT) nano-scale aggregates is negatively affected by the presence of illumination, ultimately resulting in the retardation of growth in conjugated polymer microstructures and the formation of smaller scale macro-aggregate clusters.

A protocol for the analysis of gels formed from the optoelectronic conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) using small and ultra-small angle neutron scattering in both the presence and absence of illumination is presented.

Monitoraggio degli effetti di illuminazione sulla struttura del gel di polimeri coniugati utilizzando lo Scattering di neutroni

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

Raman e IR Spettroelettrochimica metodi come strumenti per analizzare composti organici coniugati

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...