C. Matériaux étudiés
IV.4. La tenorite CuO
IV.4.a. Structure cristallographique
L’oxyde CuO ou tenorite se distingue des monoxydes de métaux de transition 3d par sa structure monoclinique. Il s’agit d’un solide ionique noir ayant comme température de fusion et d’évaporation 1064 et 1100°C respectivement. Dans cette structure, le cuivre se situe au centre de plans carrés définis par des anions oxygène (Figure I.27). La tenorite cristallise dans le groupe d’espace C2/c [129] avec des paramètres de maille définis dans le Tableau I.14.
Figure I.27. Représentation schématique de la structure cristallographique de CuO : les sphères grises représentent les ions Cu2+et les sphères rouges les ions O2-
CuO Groupe d’espace C2/c a = 4.6883 Paramètre de maille (Å) b = 3.4229 β= 99.51° c = 5.1319 Volume (Å3) 81.22
Volume molaire (cm3.mol-1) 12.21 Masse volumique (g.cm-3) 6.505
Z 4
Tableau I.14. Données cristallographiques de la tenorite [130]
IV.4.b. Propriétés électriques
L’oxyde de cuivre CuO est également un semiconducteur de type p avec un band-gap Eg compris entre 1.2 et 1.4 eV [131, 132, 133]. CuO montre généralement une faible conductivité. De grandes variations dans les valeurs de résistivité ont été reportées ainsi qu’une forte dépendance de la résistivité en fonction de la méthode d’élaboration de 1 à 107Ω.cm [134]. Les films préparés par pulvérisation ou PECVD montrent de faibles résistivités, 10 Ω.cm [135] et 0.5-5 Ω.cm [136], respectivement, qui ont été attribuées soit à
une non-stoechiométrie, soit à une conduction aux joints de grains [135]. L’évolution de la conductivité avec la température montre cependant un comportement original pouvant être utilisé en tant que composant clé pour les verres semiconducteurs [137] ou bien encore les capteurs de gaz à base de semiconducteurs [5, 138, 139, 140, 141]. Les possibles raisons de ce comportement sont : la faible quantité d’impureté dans le composé et sa stabilité en température dans une atmosphère à faible pression partielle d’oxygène.
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