Etude des catalyseurs de croissance de nanotubes de carbone monoparois synthetises par cvd

INSTITUT NATIONAL POLYTECHNIQUE DE GRENOBLE N° attribué par la bibliothèque | | | | | | | | | | | THESE pour obtenir le grade de DOCTEUR DE L’INP Grenoble Spécialité : « Science et Génie des Materiaux » préparée au laboratoire Laboratoire des Composants Hybrides dans le cadre de l’Ecole Doctorale « Matériaux et Génie des Procédés » présentée et soutenue publiquement par Van Thang LE le 26 Septembre 2008 ETUDE DES CATALYSEURS DE CROISSANCE DE NANOTUBES DE CARBONE MONOPAROIS SYNTHETISES PAR CVD DIRECTEUR DE THESE ENCADRANTS : Robert BAPTIST : Frédéric GAILLARD Emmanuelle ROUVIERE JURY M Mau Chien DANG M Didier PRIBAT M Robert BAPTIST M Quoc Tuan TRAN M Frédéric GAILLARD Mme Emmanuelle ROUVIERE Président, Rapporteur Rapporteur Directeur de thèse Examinateur Invité Invitée i ii Acknowledgements Neither these past three years in CEA/LITEN/DTNM/LCH, nor me, nor this thesis would be the same without the help and company of many people First, I wish to express my sincere appreciation to my research advisor, Professor Robert BAPTIST, for his scientific guidance and support during the course of this research work His assistance and suggestions were crucial in the realization of this work I am especially grateful to my supervisors, Dr Frederic GAILLARD and Ms Emmanuelle ROUVIERE, for always being supportive, understanding, ready to help and their suggestions Among many others, I have enjoyed your company in a social setting just as much as your scientific input in the lab Thank you for teaching me, listening to me, and letting me argue with you I couldn’t ask for better guidance I was very fortunate to get help from a lot of people in the lab, thanks for all your helps Special thanks to Pascal FAUCHERAND and Severine PONCET, who helped me for all of the technical work I also thank to my friends, Lionel FOUDRINIER, Céline MOUCHET, Nicolas KARST… for their support and friendship, and many others that I could not mention here Thanks to Mr Cyril CAYRON, Mr Alexandre MONTANI, Mr Eric de VITO and Ms Claude CHABROL for letting me used the SEM, XRD and XPS instruments, thanks to Mr Denis ROUCHON, who is the manager of the Raman engine Dr Jean-Pierre SIMONATO and Ms Aurelie THUAIRE gave me a great opportunity to work in their lab during the third year I am grateful to Vietnam National University, Ho Chi Minh City, CEA Grenoble and EGIDE for supplying a scholarship Living with people from different countries has definitely expanded my world view Thank you all for the smiles, the warmth, and making the dormitory feel like a big family And finally, most importantly, I want to thank my family and my Vietnamese friends for always quietly watching out for me, patiently loving me, and sparing advice, when I needed it most I wouldn’t be who I am if it wasn’t for you iii iv Abstract Carbon nanotubes have numerous potential applications in areas such as biotechnology, electronics, photonics and materials They can be described as graphene sheets rolled up to form a tube and exist in two forms: Single Wall Carbon Nanotube (SWCNT) and Multi Wall Carbon Nanotube (MWCNT) Three main synthesis techniques exist for CNTs, namely arcdischarge, laser ablation and chemical vapor deposition (CVD) One of that, the CVD is a promising method to grow carbon nanotubes in which typically hydrocarbon gases are dissociated on catalyst at medium temperature (600-1200°C) This thesis is focussed on the chemical vapour deposition method to produce single wall carbon nanotubes The purposes of this research are to understand exactly the role of the various chemical components presented in catalyst for the producing of SWNTs, to control process conditions, to develop synthesis techniques for SWNTs on patterned catalyst that allow the integration for electronic devices and to transfer process to industrial CVD instrument Experimental investigations are presented which allow getting a comprehensive picture of the powder catalyst growth of carbon nanotubes film The role of each element in catalyst and the optimal amount of them are illustrated Based on the electron microscopy, Raman spectroscopy, X-Ray diffraction, X-Ray photoelectron spectroscopy and microbalance results, a new component, (FexAly)(Al2-yFe1-x)O4, is detected The (FexAly)(Al2-yFe1-x)O4 provides a key role to create active nanoparticles for carbon nanotubes growth Subsequent studies of the properties of the produced carbon nanotubes grown by CVD reveal significant features of the product Based on those experimental results, a mechanism for the growth of carbon nanotubes on the powder catalyst is suggested Furthermore, a purification method of as-grown SWCNT has been developed that provides for the removal of catalyst nanoparticles and impurity carbon We note that our purified product contain ~95% wt carbon products Complementary, by varying global growth parameters such as synthesis temperature, flow ratio of carbonaceous/hydrogen gas and growth time, this study attempts to control the process condition for the synthesis high yield of SWNTs Furthermore, we present the results of the transfer of the synthesis process of SWNTs from the EASYTUBE system (small tubular CVD reactor) to industrial CENTURA tool (compatible wafer 200 mm) and the patterned growth of SWNTs for electrical devices v Keywords: Catalyst, Promoter, Active Particle, Carbon Nanotube, Chemical Vapor Deposition, Nanoparticles, Device vi RESUME Depuis plusieurs années, les nanotubes de carbone (CNT pour Carbon Nanotubes en anglais) ont fait l’objet de nombreuses études et publications sur la base de leurs extraordinaires propriétés mécanique, physique, chimique et électronique Des applications nombreuses, mettant en œuvre des nanotubes de carbone, ont vu le jour telles que : écrans plats, composants nanoélectroniques, capteurs chimiques et pointes de mesure dans les microscopes force atomique Plusieurs méthodes existent pour la fabrication des nanotubes de carbone comme l’arc électrique, l’ablation laser ou le dépôt chimique en phase vapeur (CVD pour Chemical Vapor Deposition en anglais dans le texte) Aujourd’hui, la technique CVD présente le meilleur potentiel pour la croissance des nanotubes en comparaison aux autres techniques Généralement, la méthode CVD nécessite l’utilisation d’un catalyseur, constitué d’un (ou plusieurs) métal (-aux) de transition, supporté (s) par un substrat La CVD assistée par un catalyseur est une des méthodes les plus simples pour produire de grande quantité de nanotubes de carbone L’élaboration, la structure, les propriétés et les applications des nanotubes de carbone sont encore largement étudiées Cependant, le choix des méthodes de synthèse et la compréhension des mécanismes de croissance des nanotubes ne sont pas complètement aboutis alors qu’ils sont les clés de la réussite d’un contrôle des propriétés des nanotubes produits ainsi que de leur rendement de production Il reste notamment explorer le rôle de chacun des constituants du catalyseur pendant la phase de nucléation et l’évolution de ce catalyseur pendant la croissance des nanotubes de carbone Ces travaux de thèse portent sur la mise en œuvre de méthode CVD pour l’élaboration de nanotubes de carbone mono paroi (SWCNT pour Single Wall Carbon Nanotubes en anglais dans le texte) Le but de cette recherche est d’une part, de comprendre le rôle de chacun des constituants du catalyseur permettant la croissance des SWCNT Le mécanisme de croissance des SWCNT sera déduit de ces explications D’autre part, une étude paramétrique du procédé de croissance des SWCNT portant sur l’évolution des conditions exploratoires telles que la température de synthèse, le rapport des gaz réactifs (Hydrocarbure/Hydrogène) et la durée du procédé, a permis de déterminer les conditions optimisées de CVD assistée par catalyseur , pour l’élaboration de SWCNT Les propriétés des SWCNT ont également été explorées en vue de leur utilisation potentielle dans des composants électroniques vii Après un premier chapitre d’introduction générale, le second chapitre fait l’objet d’une étude bibliographique portant principalement sur les différents modes de synthèse des nanotubes de carbone et de préparation des catalyseurs pour la technique CVD assistée par catalyseur Le troisième chapitre présente l’étude de la formulation chimique du catalyseur exploité pour la croissance des SWCNT et le rôle de chacun de ces constituants Les propriétés physico-chimiques des SWCNT produits et le mécanisme de croissance de SWCNT sont exposées dans le quatrième chapitre C’est également dans cette partie qu’une méthode de purification des SWCNT produits est enfin proposée en vue de l’exploitation de ces SWCNT dans des applications électroniques Le cinquième chapitre porte d’une part, sur le transfert de procédé d’un réacteur de laboratoire (EASYTUBE) dans un réacteur industriel compatible avec des tailles de wafers de 200mm (CENTURA) et d’autre part, sur l’étude de la localisation du catalyseur et donc, des nanotubes, pour la fabrication de composants électroniques Ce manuscrit est conclu par une conclusion générale et les perspectives donner ces travaux de thèse I- Etude du catalyseur de croissance de nanotubes de carbone monoparois Afin d’étudier le rôle de chacun des constituants du système catalytique, des expériences systématiques ont été reproduites dans le réacteur CVD de synthèse de SWCNT Ces investigations expérimentales ont permis de comprendre le rôle des constituants du catalyseur de croissance des SWCNT Les images réalisées en microscopie électronique balayage (MEB) reportées dans la figure montrent le type de produit obtenu après l’étape de croissance de CNT pour des compositions extrêmes Une grande quantité de nanotubes est visible sur l’image a- de la fig.1 dans le cas où le catalyseur dit « standard » est composé des trois éléments, fer, molybdène et alumine Il est observé une relativement faible quantité de CNT sur l’image c- en l’absence de molybdène dans le catalyseur Enfin, aucun CNT n’est observé sur les images b- et d- en l’absence respectivement d’alumine et de fer L’absence de CNT dans le cas b est attribuée la coalescence des particules métalliques contenues dans le catalyseur la température de procédé (900°C) et dans le cas d-, l’absence de l’élément fer viii (a) (b) (c) (d) Fig.1: Images MEB des surfaces d’échantillons après le procédé de croissance de CNT par CVD (a) Catalyseur “Standard” (Al2O3, Fe2O3, MoO3), (b) Catalyst exempt d’ Al2O3, (c) Catalyst exempt de Molybdène et (d) Catalyst sans fer La croissance de SWCNT est confirmée par spectrométrie Raman réalisée sur les deux échantillons d’intérêt (fig 2), notés TFe (voir fig.1-c) et T1 (voir fig.1-a) présentant trois caractéristiques types dans le spectre : - des pics dans le mode RBM (Radial Breathing Mode) dans la gamme 130-300cm-1, - un pic dans le mode TM (Tangential Mode) dans la gamme 1560-1600cm-1 présentant le type de graphitisation (noté G) du produit analysé, et - un pic dans le mode D (Disorder) dans la gamme 1320-1380 cm-1, relatif la présence de carbone amorphe et défaut cristallin dans les nanotubes de carbone produits ix 1600 4000 TFeLF TMoLF T1LF 1400 3500 3000 Intensity (a.u.) Intensity (a.u.) 1200 TFeHF TMoHF T1HF 1000 800 600 2500 2000 1500 400 1000 200 500 0 100 150 200 250 300 350 1200 Frequency (cm-1) 1300 1400 1500 1600 Frequency (cm-1) Fig 2: Spectres Raman réalisés sur les CNT produits par CVD partir de différents catalyseurs pour de faible nombre d’ondes (gauche) et nombre d’onde élevé (droite) La superposition du spectre TMo, exempt de pics RBM et G, obtenu sur un échantillon après procédé de croissance partir d’un catalyseur constitué de molybdène et d’alumine, confirme l’unique présence de carbone amorphe la surface de l’échantillon traité L’analyse par spectrométrie de photoélectron X (XPS) du catalyseur « standard » constitué de Fe, Al2O3 et Mo après un cycle de température 900°C, révèle notamment (fig 3) : - la présence de fer, de molybdène et d’alumine - les états d’oxydation du fer et du molybdène, qui sont respectivement sous la forme de Fe2O3 et MoO3 Fig 3: Spectre XPS obtenu partir d’un échantillon de catalyseur « standard » ayant subi un cycle thermique 900°C sous hydrogène L’analyse par diffraction des rayons X (DRX) du catalyseur « standard » constitué de Fe, Al2O3 et Mo après un cycle de température 900°C, révèle la formation d’un nouveau x [16] S Iijima and T Ichihashi Single-shell carbon nanotubes of 1-nm diameter Nature 363 (1993), 603 [17] D S Bethune, C-H Kiang, R D Johnson, J R Salem, M S De Vries, G Gorman, R Savoy, J Vazquez R Beyers & C S Yannoni Cobalt-Catalysed Growth of Carbon Nanotubes with Single-Atomic-Layer Walls Nature 363, (1993), 605-607 [18] A Thess, R Lee, P Nikolaev, H J Dai, P Petit, J Robert, C H Xu, Y H Lee, S G Kim, A G Rinzler, D T Colbert, G E Scuseria, D Tomanek, J E Fischer and R E Smalley, Crystalline Ropes of Metallic Carbon Nanotubes Science, 273 (1996), 483-487 [19] M J Yacaman, M M Yoshida, L Rendon, Catalytic growth of carbon microtubules with fullerene structure Appl Phys Lett 62 (1993), pages [20] R Saito, G Dresselhaus, M S Dresselhaus Physical Properties of carbon nanotubes Imperial College Press 1998 [21] Michael J O’Connell Carbon nanotubes properties and applications Taylor & Francis, 2006 [22] M M J Treacy T W Ebbesen & J M Gibson Exceptionally high Young's modulus observed for individual carbon nanotubes Nature 381 (1996), 678 - 680 [23] M F Yu, O Lourie, M J Dyer, K Moloni, T F Kelly, R S Ruoff Strength and Breaking Mechanism of Multiwalled Carbon Nanotubes Under Tensile Load Science 287 (2000), 637 – 640 [24] M Arroyo and T Belytschko Nonlinear Mechanical Response and Rippling of Thick Multiwalled Carbon Nanotubes Phys Rev Lett 91(2003), 215505 [25] B I Yakobson and Ph Avouris Mechanical Properties of Carbon Nanotubes Springer Berlin / Heidelberg, 80 (2001), 287-327 [26] J W Mintmire, B I Dunlap, and C T White Are fullerene tubules metallic? 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part, une étude paramétrique du procédé de croissance des SWCNT portant sur l’évolution des conditions exploratoires telles que la température de synthèse, le rapport des gaz réactifs (Hydrocarbure/Hydrogène) et la durée du procédé, a permis de déterminer les conditions optimisées de CVD assistée par catalyseur , pour l’élaboration de SWCNT Les propriétés des SWCNT ont également été explorées en vue de leur utilisation potentielle dans des composants électroniques Après un premier chapitre d’introduction générale, le second chapitre fait l’objet d’une étude bibliographique portant principalement sur les différents modes de synthèse des nanotubes de carbone et de préparation des catalyseurs pour la technique CVD assistée par catalyseur Le troisième chapitre présente l’étude de la formulation chimique du catalyseur exploité pour la croissance des SWCNT et le rôle de chacun de ces constituants Les propriétés physico-chimiques des SWCNT produits et le mécanisme de croissance de SWCNT sont exposées dans le quatrième chapitre C’est également dans cette partie qu’une méthode de purification des SWCNT produits est enfin proposée en vue de l’exploitation de ces SWCNT dans des applications électroniques Le cinquième chapitre porte d’une part, sur le transfert de procédé d’un réacteur de laboratoire (EASYTUBE) dans un réacteur industriel compatible avec des tailles de wafers de 200mm (CENTURA) et d’autre part, sur l’étude de la localisation du catalyseur et donc, des nanotubes, pour la fabrication de composants électroniques Ce manuscrit est conclu par une conclusion générale et les perspectives donner ces travaux de thèse Mots-Clés : Catalyse, Promoteur, Activateur, Nanotube de carbone, Dépôt chimique partir d’une phase vapeur (CVD), nanoparticules Abstract This thesis is focussed on the chemical vapour deposition method to produce single wall carbon nanotubes The purposes of this research are to understand exactly the role of the various chemical components presented in catalyst for the producing of SWNTs, to control process conditions, to develop synthesis techniques for SWNTs on patterned catalyst that allow the integration for electronic devices and to transfer process to industrial CVD instrument Experimental investigations are presented which allow getting a comprehensive picture of the powder catalyst growth of carbon nanotubes film The role of each element in catalyst and the optimal amount of them are illustrated Based on the electron microscopy, Raman spectroscopy, X-Ray diffraction, X-Ray photoelectron spectroscopy and microbalance results, a new component, (FexAly)(Al2-yFe1-x)O4, is detected Subsequent studies of the properties of the produced carbon nanotubes grown by CVD reveal significant features of the product Based on those experimental results, a mechanism for the growth of carbon nanotubes on the powder catalyst is suggested Furthermore, a purification method of as-grown SWCNT has been developed that provides for the removal of catalyst nanoparticles and impurity carbon Complementary, by varying global growth parameters such as synthesis temperature, flow ratio of carbonaceous/hydrogen gas and growth time, this study attempts to control the process condition for the synthesis high yield of SWNTs Furthermore, we present the results of the transfer of the synthesis process of SWNTs from the EASYTUBE system (small tubular CVD reactor) to industrial CENTURA tool (compatible wafer 200 mm) and the patterned growth of SWNTs for electrical devices Keywords : Catalyst, Promoter, Active Particle, Carbon Nanotube, Chemical Vapor Deposition, Nanoparticles 164 ... méthodes de synthèse et la compréhension des mécanismes de croissance des nanotubes ne sont pas complètement aboutis alors qu’ils sont les clés de la réussite d’un contrôle des propriétés des nanotubes. .. du procédé de croissance des SWCNT d’un réacteur tubulaire de laboratoire un réacteur de type industriel, permettant de traiter des wafers de 200mm, une xviii étude des paramètres de croissance. .. différents modes de synthèse des nanotubes de carbone et de préparation des catalyseurs pour la technique CVD assistée par catalyseur Le troisième chapitre présente l’étude de la formulation