Enhanced Raman signatures on copper based-materials Deniz Cakir To cite this version: Deniz Cakir. Enhanced Raman signatures on copper based-materials. Other [cond-mat.other]. Uni- versité Montpellier, 2017. English. NNT : 2017MONTS066. tel-01944233 HAL Id: tel-01944233 https://tel.archives-ouvertes.fr/tel-01944233 Submitted on 4 Dec 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE POUR OBTENIR LE GRADE DE DOCTEUR DE L’UNIVERSITÉ DE MONTPELLIER En : Physique École doctorale : Information Structure et Systèmes (I2S) Unité de recherche : Laboratoire Charles Coulomb ENHANCED RAMAN SIGNATURES ON COPPER BASED-MATERIAL Présentée par Deniz CAKIR Le 20 décembre 2017 Sous la direction d’Éric Anglaret et de Nicole Fréty RAPPORT DE GESTION Devant le jury composé de 2015 Marc LAMY de la CHAPELLE, Professeur des Universités, Le Mans Université Rapporteur Pascal PUECH, Maître de conférences, Université Toulouse III Rapporteur Dominique BARCHIESI, Professeur des universités, Université de Technologie de Troyes Examinateur Matthias DAMMASCH, Ingénieur, Atotech Deutschland GmbH Examinateur Loïc FAVERGEON, Maitre de conférences, École Nationale Supérieure des Mines de Saint-Étienne Examinateur Nicole FRETY, Professeur des universités, Université de Montpellier Co-directrice Éric ANGLARET, Professeur des universités, Université de Montpellier Directeur Lucyna FIRLEJ, Professeur des universités, Université de Montpellier Présidente du jury Table of contents Remerciements .................................................................................................................... 1 Introduction ......................................................................................................................... 3 Chapter I: Literature ....................................................................................................... 5 1. Copper and its oxides ............................................................................................... 5 1.1. Structural properties .......................................................................................... 5 1.1.1. Crystalline structure of copper ................................................................... 5 1.1.2. Crystalline structures of most common copper oxides .............................. 5 1.2. Major structural defects in Cu2O....................................................................... 7 1.3. Electronic and optical properties ....................................................................... 8 1.3.1. Electronic properties .................................................................................. 8 1.3.2. Optical properties ....................................................................................... 9 2. Copper oxidation mechanisms and kinetics ........................................................... 13 2.1. Thermodynamic approach ............................................................................... 13 2.2. Kinetic approach ............................................................................................. 14 2.2.1. Copper oxidation kinetics at high temperature (>600°C) ........................ 14 2.2.2. Copper oxidation kinetics at low temperature (<600°C) ......................... 15 2.3. Influence of experimental parameters on oxidation kinetics .......................... 17 2.3.1. Influence of the crystalline orientation .................................................... 17 2.3.2. Influence of the temperature .................................................................... 18 Rapport de gestion 2.3.3. Influence of oxygen partial pressure ........................................................ 18 2.4. Cuprous oxide film growth ............................................................................. 19 2015 2.5. Cu2O/ CuO predominance............................................................................... 21 3. Generalities on light- matter interaction ................................................................. 21 3.1. Light ................................................................................................................ 21 3.2. Light-mater interactions .................................................................................. 22 3.1. Transmittance of a thick layer with parallel faces .......................................... 23 4. Raman spectroscopy ............................................................................................... 25 4.1. Theory ............................................................................................................. 25 4.2. Scattering in a wave perspective ..................................................................... 25 4.2.1. Scattering in a quantum perspective ........................................................ 26 4.2.2. Selection rule for first and second order Raman...................................... 26 4.3. Raman intensities ............................................................................................ 27 4.3.1. General equation ...................................................................................... 27 i 4.3.2. Resonance Raman scattering ................................................................... 28 4.3.3. Vibrational properties of copper oxide .................................................... 29 4.3.4. Vibrational properties of Raman probes ................................................. 32 4.3.5. Interference enhanced Raman Scattering (IERS) .................................... 36 5. Surface enhanced Raman spectroscopy (SERS) .................................................... 40 5.1. Physical background on light – metal interactions ......................................... 41 5.1.1. Polarizability, and relative permittivity ................................................... 41 5.1.2. Plasmon definitions ................................................................................. 41 5.1.3. Optical properties of metals .................................................................... 42 5.2. Localized surface plasmon resonance and local fields ................................... 44 5.2.1. Influence of the size and shape................................................................ 44 5.2.2. Coupling of nanoparticles ....................................................................... 47 5.3. Effective metals for SERS .............................................................................. 48 5.4. Probe for SERS ............................................................................................... 49 5.5. Enhancement factor ........................................................................................ 50 5.6. SERS on copper .............................................................................................. 51 Chapter II: Materials and methods ................................................................................ 55 1. Copper and copper oxide reference samples.......................................................... 55 2. Copper and copper oxide calibration thin films ..................................................... 56 2.1. Calibration of copper thin films ...................................................................... 56 2.2. Calibration of copper oxide thin film ............................................................. 57 3. SERS substrates ..................................................................................................... 59 3.1. Electroless copper substrates .......................................................................... 59 3.2. Etched copper substrates................................................................................. 60 3.3. Gold based substrates ..................................................................................... 61 4. Raman probes ......................................................................................................... 62 4.1. Graphene probe ............................................................................................... 62 4.2. Organic molecules probes............................................................................... 62 5. Characterization techniques ................................................................................... 63 5.1. SEM / AFM observations ............................................................................... 63 5.2. XPS chemical analyses ................................................................................... 65 5.2.1. XPS principle .......................................................................................... 65 5.2.2. XPS experiments ..................................................................................... 66 5.3. Ellipsometry .................................................................................................... 68 5.3.1. Multiple angle of incidence (MAI) ellipsometry .................................... 70 5.3.2. Spectroscopic ellipsometry.....................................................................