In this diploma thesis, SERRS(Surface - enhanced resonance Raman Scattering) and SERS (Surface - enhanced Raman Scattering), surface of plasmon extinction spectra and TEM images of systems with tetracationic zinc porphyrin ZnTMPyP and silver nanoparticles (Ag NPs) were studied and interpreted. The systems with isolated nanoparticles and the systems with compact aggregates were investigated. The systems with isolated nanoparticles were prepared by addition of ZnTMPyP to hydrosol of Ag NPs. NaCl was added to this system and so compact aggregates were prepared. SERRS and SERS spectra of ZnTMPyP were studied at excitation wavelengths λexc= 441.6 nm a 532 nm. Firstly, stationary systems and secondly dynamic development of hydrosol Ag NPs → Ag NPs/ ZnTMPyP → Ag NPs/ ZnTMPyP/ NaCl systems for 680 s was investigated. Time evolution of SERRS and SERS spectra were analyzed by factor analysis (FA) and time evolution of spectra extinction plasmon were measured. FA showed a strong increase of the signal of ZnTMPyP after the addition of NaCl, i.e. after conversion of isolated nanoparticles to compact aggregates. In these systems with high concentration of ZnTMPyP the increase of signal was succeeded by its decreased. With help of FA the limit of SERRS spectral detection (λexc= 441,6 nm) and limit of SERS spectral...

Im ersten Teil der Arbeit werden Signalverstärkungsmechanismen für Raman-Spektroskopie erschlossen und evaluiert. Die als geeignet bewerteten Methoden finden im zweiten Teil ihre Anwendung zur Untersuchung der vibronischen Eigenschaften von dünnen Manganphthalocyaninschichten, die anschließend mit Kalium interkaliert werden. Hierbei sind verschiedene Phasen identifizierbar, die ein ganzzahliges Verhältnis von Kaliumatomen zu Manganphthalocyaninmolekülen besitzen. Im dritten Teil werden die elektrischen Eigenschaften durch die Verwendung dieses Materialsystems als aktives Medium eines Feldeffekttransistors untersucht.:1. Einleitung 2. Theoretische Grundlagen der angewendeten Effekte 3. Experimentelle Details 4. Herstellung, Charakterisierung und Optimierung von Substraten für Raman-Oberflächenverstärkungseffekte 5. Untersuchung zu Verstärkungsmechanismen des Raman-Effekts an dünnen organischen Schichten 6. Interkalation mit Kalium in dünne Schichten aus Manganphthalocyanin 7. MnPc unter Spannungs- und Stromeinfluss - Der Feldeffekttransistor 8. Zusammenfassung Anhang Literatur Abbildungsverzeichnis Eidesstattliche Versicherung Lebenslauf Liste wissenschaftlicher Leistungen Danksagung

The thesis presents experimental studies of device characteristics and vibrational properties of atomic layer thin graphene and molybdenum disulphide (MoS2). We carried out Raman spectroscopic studies on field effect transistors (FET) fabricated from these materials to investigate the phonons renormalized by carrier doping thus giving quantitative information on electron-phonon coupling. Below, we furnish a synoptic presentation of our work on these systems. Chapter1: Introduction Chapter1, presents a detailed introduction of the systems studied in this the¬sis, namely single layer graphene (SLG), bilayer graphene (BLG) and single layer molybdenum disulphide (MoS2). We have mainly discussed their electronic and vibrational properties in the light of Raman spectroscopy. A review of the Raman studies on graphene layers is presented. Chapter2: Methodology and Experimental Techniques Chapter 2 starts with a description of Raman instrumentation. The steps for isolating graphene and MoS 2 flakes and the subsequent device fabrication procedures involving lithography are discussed in detail. A brief account of the top gated field effect transistor (FET) using solid polymer electrolyte is presented. Chapter3: Band gap opening in bilayer graphene and formation of p-n junction in top gated graphene transistors: Transport and Raman studies In Chapter3 the bilayer graphene (BLG) field effect transistor is fabricated in a dual gate configuration which enables us to control the energy band gap and the Fermi level independently. The gap in bilayer energy spectrum is observed through different values of the resistance maximum in the back gate sweep curves, each taken at a fixed top gate voltage. The gate capacitance of the polymer electrolyte is estimated from the experimental data to be 1.5μF/cm2 . The energy gap opened between the valence and conduction bands using this dual-gated geometry is es¬timated invoking a simple model which takes into account the screening of gate induced charges between the two layers. The presence of the controlled gap in the energy band structure along with the p-n junction creates a new possibility for the bilayer to be used as possible source of terahertz source. The formation of p-n junction along a bilayer graphene (BLG) channel is achieved in a electrolytically top gated BLG FET, where the drain-source voltage VDS across the channel is continuously varied at a fixed top gate voltage VT(VT>0). Three cases may arise as VDS is varied keeping VT fixed: (i) for VT-VDS0, the entire channel is doped with electron, (ii) for VT-VDS= 0, the drain end becomes depleted of carriers and kink in the IDS vs VDS curve appears, (iii) for VT-VDS « 0, carrier reversal takes place at the drain end, accumulation of holes starts taking place at the drain end while the source side is still doped with electrton. The verification of the spatial variation of carrier concentration in a similar top gated single layer graphene (SLG) FET device is done using spatially resolved Ra¬man spectroscopy. The signature 2D Raman band in a single layer graphene shows opposite trend when doped: 2D peak position decreases for electron doping while it increases for hole doping. On the other hand, the G mode response being symmetric in doping can act as a read-out for the carrier concentration. We monitor the peak position of the G and the 2D bands at different locations along the SLG FET channel. For a fixed top gate voltage V T , both G and the 2D band frequencies vary along the channel. For a positive VTsuch that VT-VDS= 0, the peak frequencies ωGand ω2DωG/2D occur at the undoped frequency (ωG/2D)n=0 near the drain end while the source end corresponds to non-zero concentration. When VT-VDS<0, Raman spectra from hole doped regions (drain end) in the channels show an blue-shift in ω2Dwhile from the electron doped regions (near source) ω2Dis softened. Chapter4: Mixing Of Mode Symmetries In Top Gated Bilayer And Multilayer Graphene Field Effect Devices In Chapter4, the effect of gating on a bilayer graphene is captured by using Raman spectroscopy which shows a mixing of different optical modes belonging to differ¬ent symmetries. The zone-center G phonon mode splits into a low frequency (Glow) and a high frequency (Ghigh) mode and the two modes show different dependence on doping. The two G bands show different trends with doping, implying different electron-phonon coupling. The frequency separation between the two sub-bands in¬creases with increased doping. The mode with higher frequency, termed as Ghigh, shows stiffening as we increase the doping whereas the other mode, Glow, shows softening for low electron doping and then hardening at higher doping. The mode splitting is explained in terms of mixing of zone-center in-plane optical phonons rep¬resenting in-phase and out-of-phase inter-layer atomic motions. The experimental results are combined with the theoretical predictions made using density functional theory by Gava et al.[PRB 80, 155422 (2009)]. Similar G band splitting is observed in the Raman spectra from multilayer graphene showing influence of stacking on the symmetry properties. Chapter5: Anomalous dispersion of D and 2D modes in graphene and doping dependence of 2D ′and 2D+G bands Chapter 5 consists of two parts: Part A titled “Doping dependent anomalous dispersion of D and 2D modes in graphene” describes the tunability of electron-phonon coupling (EPC) associated with the highest optical phonon branch (K-A) around the zone corner K using a top gated single layer graphene field effect transistor. Raman D and 2D modes originate from this branch and are dispersive with laser excitation energy. Since the EPC is proportional to the slope of the phonon branch, doping dependence of the D and 2D modes is carried out for different laser energies. The dispersion of the D mode decreases for both the electron and the hole doping, in agreement with the recent theory of Attaccalite et. al [Nano Letters, 10, 1172 (2010)]. In order to observe D-band in the SLG samples, low energy argon ion bombardment was carried out. The D peak positions for variable carrier concentration using top-gated FET geometry are determined for three laser energies, 1.96 eV, 2.41 eV and 2.54 eV. However, the dispersion of the 2D band as a function of doping shows an opposite trend. This most curious result is quantitatively explained us¬ing a fifth order process rather than the usual fourth order double resonant process usually considered for both the D and 2D modes. Part B titled “Raman spectral features of second order 2D’ and 2D+G modes in doped graphene transistor” deals with doping dependence of 2D’ and 2D+G bands in single layer graphene transistor. The phonon frequency blue shifts for the hole doping and whereas it red shifts for electron doping, similar to the behaviour of the 2D band. The linewidth of the 2D+G combination mode too follows the 2D trend increasing with doping while that of 2D’ mode remains invariant. Chapter6: New Raman modes in graphene layers using 2eV light Unique resonant Raman modes are identified at 1530 cm−1 and 1445 cm−1 in single, bi, tri and few layers graphene samples using 1.96 eV (633 nm) laser excitation energy (EL). These modes are absent in Raman spectra using 2.41 eV excitation energy. In addition, the defect-induced D band which is observed only from the edges of a pristine graphene sample, is observed from the entire sample region using E L = 1.96 eV. Raman images with peak frequencies centered at 1530 cm−1, 1445 cm−1 and D band are recorded to show their correlations. With 1.96 eV, we also observe a very clear splitting of the D mode with a separation of ∼32 cm−1, recently predicted in the context of armchair graphene nanoribbons due to trigonal warping effect for phonon dispersion. All these findings suggest a resonance condition at ∼2eVdue to homo-lumo gap of a defect in graphene energy band structure. Chapter7: Single and few layer MoS2: Resonant Raman and Phonon Renormalization Chapter 7 is divided into two parts. In Part A “Layer dependent Resonant Raman scattering of a few layer MoS2”, we discuss resonant Raman scattering from single, bi, four and seven layers MoS2. As bulk crystal of MoS2is thinned down to a few atomic layers, the indirect gap widens turning into a direct gap semiconductor with a band gap of 1.96 eV in its monolayer form. We perform Raman study from MoS 2 layers employing 1.96 eV laser excitation in order to achieve resonance condition. The prominent Raman modes for MoS 2 include first order E12g mode at ∼383 cm−1 and the A1gmode at ∼408 cm−1 which are observed under both non resonant and resonant conditions. A1gphonon involves the sulphur atomic vibration in opposite direction along the c axis (perpendicular to the basal plane) whereas for E12g mode, displacement of Mo and sulphur atoms are in the basal plane. With decreasing layer thickness, these two modes shifts in opposite direction, the E12g mode shows a blue shift of ∼2cm−1 while the A1gis red shifted by ∼4cm−1 . Under resonant condi¬tion, apart from E12g and A1gmodes, several new Raman spectral features, which are completely absent in bulk, are observed in single, bi and few layer spectra pointing out the importance of Raman characterization. New Raman mode attributed to the longitudinal acoustic mode belonging to the phonon branch at M along the Γ-M direction of the Brillouin zone is seen at ∼230 cm−1 for bi, four and seven layers. The most intense region of the spectrum around 460 cm−1 is characterized by layer dependent frequencies and spectral intensities with the band near 460 cm−1 becoming asymmetric as the sample thickness is increased. In the high frequency region between 510-630 cm−1, new bands are seen for bi, four and seven layers. In Part B titled “Symmetry-dependent phonon renormalization in monolayer MoS2transistor”, we show that in monolayer MoS2the two Raman-active phonons, A1g and E21 g, behave very differently as a function of doping induced by the top gate voltage in FET geometry. The FET achieves an on-off ratio of ∼ 105 for electron doping. We show that while E12g phonon is essentially unaffected, the A1gphonon is strongly influenced by the level of doping. We quantitatively understand our experimental results through the use of first-principles calculations to determine frequencies and electron-phonon coupling for both the phonons as a function of carrier concentration. We present symmetry arguments to explain why only A1g mode is renormalized significantly by doping. Our results bring out a quantitative under¬standing of electron-phonon interaction in single layer MoS2.

Nous avons étudiés des fils quantiques dopés de semi-conducteurs gravés par spectroscopie de diffusion Raman. Nous avons observés les excitations du gaz d'électrons. Celles-ci présentent des règles de sélection différentes de celles établies pour les systèmes bi-dimensionnels. Nous avons montré théoriquement qu'elles proviennent de la modification de la structure du champ électromagnétique local provoquée par la géométrie particulière des fils gravés. Pour cela nous avons dû calculer le champ local et l'introduire dans la section efficace de diffusion Raman pour en déduire les règles de sélection de toutes les excitations. Cela a permis de déterminer sans équivoque la nature des excitations qui sont des plasmons. Aucune excitations à une particule ni fluctuations de densité de spin n'a été observées. Nous avons étudié l'évolution continue des dispersions de ces plasmons lorsque la largeur du fil est réduite de 1 micromètre à 30 nm. Jusqu'à 60 nm, celles-ci sont en très bon accord avec les résultats d'un modèle hydrodynamique. Au dessous de 60 nm, la comparaison avec un modèle RPA s'impose. Le plasmon intra-bande dispersif est observé jusqu'à 45 nm, largeur en dessous de laquelle les spectres Raman sont dominés par des excitations localisées qui nécessitent une analyse ultérieure pour en déterminer clairement leur nature. Nous montrons à l'aide du modèle RPA que nous avons atteint la limite quantique pour un fil de largeur 55 nm. Une gamme étroite de fils dont les largeurs sont comprises entre 55 nm à 45 nm permet donc l'étude de gaz strictement unidimensionnel.<br />Nous avons cherché à déterminer la contribution de la forte illumination dans les conclusions précédentes. Nous avons utilisé pour cela la spectroscopie de magnéto-transmission infra-rouge qui ne modifie pas les conditions d'équilibre du gaz d'électrons. Une largeur critique de 130 nm a été extraite, en dessous de laquelle nous n'avons plus aucun signe de la présence d'électrons libres. La comparaison des mesures Raman et infra-rouge a permis l'établissement et la validation d'un modèle microscopique du potentiel de confinement présent dans les fils. Enfin nous avons fabriqués des échantillons de géométries plus complexes. L'observation et l'analyse par diffusion Raman des plasmons dans ces fils a montré que nous pouvions contrôler la géométrie du potentiel confinant les électrons et a mis en évidence des effets nouveaux tels que le repliement et le confinement de plasmons unidimensionnels.

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb2) in triplet states formed on the surface of superfluid helium nanodroplets is investigated both experimentally and theoretically. Detailed comparison of experimental femtosecond pump–probe spectra with dissipative quantum dynamics simulations reveals that vibrational relaxation is the main source of dephasing. The rate constant for vibrational relaxation in the first excited triplet state 13Σ+g is found to be constant γ ≈ 0.5 ns−1 for the lowest vibrational levels v [less, similar] 15 and to increase sharply when exciting to higher energies. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

This work describes a master’s thesis in engineering physics at Umeå University carried out during the spring semester of 2014. In the thesis the student has constructed and tested a temperature controlled cell for cooling/heating of surface-enhanced-Raman-spectroscopy (SERS) substrates for rapid detection of volatile substances. The thesis was carried out at the Swedish Defence Research Agency (FOI) in Umeå, Sweden. A Linkam Scientific Instruments TS1500 cell was equipped with a Peltier element for cooling/heating and a thermistor temperature sensor. A control system was constructed, based on an Arduino Uno microcontroller board and a pulse-width-modulated (PWM) H-bridge motor driver to control the Peltier element using a proportional-integral (PI) control algorithm. The temperature controlled cell was able to regulate the temperature of a SERS substrate within -15 to +110 °C and maintain the temperature over prolonged periods at ±0.22 °C of the set point temperature. Gas phase of 2-chloro-2-(difluoromethoxy)-1,1,1-trifluoro-ethane (isoflurane) was flowed through the cell and SERS spectra were collected at different temperatures and concentrations. This test showed that the signal is increased when the substrate is cooled and reversibly decreased when the substrate was heated. Keywords: temperature control, Raman scattering, surface enhanced Raman spectroscopy SERS, SERS substrate, volatile substances, Peltier module, thermistor, PWM, H-bridge, PI(D) control. / Detta dokument beskriver ett examensarbete för civilingenjörsexamen i teknisk fysik vid Umeå Universitet som utförts under vårterminen 2014. I examensarbetet har en kyl-/värmecell för temperaturkontroll av substratytor för ytförstärkt ramanspektroskopi (SERS) för snabb detektion av farliga flyktiga ämnen konstruerats och testats. Arbetet utfördes vid Totalförsvarets forskningsinstitut (FOI) i Umeå, Sverige. Utgångspunkten var ett Linkam Scientific Instruments TS1500 mikroskopsteg, vilket utrustades med ett Peltierelement för kylning/värmning och en termistor för temperaturövervakning. Ett styrsystem baserat på ett Arduino Uno mikrostyrenhetskort konstruerades med ett motordrivkort (H-brygga) vilket använder pulsbreddsmodulering (PWM) för att reglera spänningen till Peltierelementet utifrån en PI-regulator. Den färdiga cellen klarade att reglera temperaturen på ett SERS-substrat i ett temperaturspann på ungefär -15 till +110 °C med en temperaturstabilitet på ±0.22 °C av måltemperaturen. Cellen testades sedan på flyktiga ämnen för att visa dess funktion. Difluorometyl-2,2,2-trifluoro-1-kloroetyleter (isofluran) i gasfas, med instrumentluft som bärargas, flödades genom cellen och SERS-spektra erhölls vid olika koncentrationer och temperaturer. Vid samtliga koncentrationer visades att lägre temperatur ger ökad signalstyrka. När ytan sedan värmdes upp sjönk signalen reversibelt tillbaka till ursprungsvärdet. Nyckelord: temperaturkontroll, ytförstärkt ramanspektroskopi, SERS, flyktiga ämnen, Peltierelement, thermistor, PWM, H-brygga, PI(D)-regulator.

La concentration locale des messagers chimiques sécrétés par les cellules peut être mesurée afin de mieux comprendre les mécanismes moléculaires liés à diverses maladies, dont les métastases du cancer. De nouvelles techniques analytiques sont requises pour effectuer ces mesures locales de marqueurs biologiques à proximité des cellules. Ce mémoire présentera le développement d’une nouvelle technique basée sur la réponse plasmonique sur des leviers AFM, permettant d’étudier les réactions chimiques et biologiques à la surface des leviers grâce au phénomène de résonance des plasmons de surface (SPR), ainsi qu’à la diffusion Raman exaltée par effet de pointe (TERS). En effet, il est possible de localiser l’amplification du signal Raman à la pointe d’un levier AFM, tout comme le principe de la diffusion Raman exaltée par effet de surface (SERS) basée sur la diffusion de la lumière par des nanoparticules métalliques, et permettant une large amplification du signal Raman. La surface du levier est recouverte d’une nano-couche métallique d’or, suivi par des réactions biologiques pour l’immobilisation d’un récepteur moléculaire, créant ainsi un biocapteur sur la pointe du levier. Une détection secondaire utilisant des nanoparticules d’or conjuguées à un anticorps secondaire permet également une amplification du signal SPR et Raman lors de la détection d’antigène. Ce mémoire démontrera le développement et la validation de la détection de l’immunoglobuline G (IgG) sur la pointe du levier AFM.Dans des projets futurs, cette nouvelle technique d’instrumentation et d’imagerie sera optimisée grâce à la création d’un micro-détecteur protéique généralement adapté pour l’étude de la communication cellulaire. En intégrant le signal SPR à la microscopie AFM, il sera alors possible de développer des biocapteurs SPR couplés à une sonde à balayage, ce qui permettra d’effectuer une analyse topographique et de l’environnement chimique d’échantillons cellulaires en temps réel, pour la mesure des messagers moléculaires sécrétés dans la matrice extracellulaire, lors de la communication cellulaire. / Measurement of the local concentration of chemical messengers secreted by cells may give a better understanding of molecular mechanisms related to different diseases, such as cancer metastasis. Current techniques are not suited to perform such measurements and thus, new analytical techniques must be developed. This Master’s thesis reports the development of a new technique based on the plasmonic response of atomic force microscopy (AFM) tips, which will ultimately allow monitoring of chemical and biological molecules on the surface of a cantilever by use of surface plasmon resonance (SPR) and tip-enhanced Raman scattering (TERS). Indeed, it is possible to localize the enhancement of the Raman signal on the AFM tip using principles associated to surface-enhanced Raman spectroscopy (SERS), based on the absorption of light by nanometer-sized metal particles, resulting in a large enhancement of the Raman signal. The AFM tip was constructed by the deposition of a nanometer-size gold layer, followed by the assembly of a biosensor with a biomolecular receptor. Gold nanoparticles (AuNPs) conjugated with a secondary antibody served as the secondary detection step. In addition, the use of the gold nanoparticles for antigen detection allows an amplification of the SPR and Raman signals. This Master’s thesis will demonstrate the development and validation of a biosensor for immunoglobuline G (IgG) at the tip of an AFM cantilever.This thesis sets the basis for future projects, where this new imaging technique will be developed for monitoring cellular communication by exploiting the plasmonic signal at the AFM tip. Different biosensors will then be developed and coupled to an AFM probe for scanning the chemical environment and detect in real-time chemical messengers secreted in the extracellular matrix in cellular communication.

Pour mieux appréhender les mécanismes de transfert des gaz (CO2 et CH4) dissous dans l’eau porale des formations des marnes du site de Bure et des argiles à Opalinus (AOP) du Mt Terri dans leur état initial, un capteur infrarouge (IRTF) et un banc optique Raman innovant ont été développés et installés en laboratoire souterrain. Ces capteurs sont intégrés au dispositif de l’expérimentation « d’équilibration de gaz » développée par l’Andra (PAC) qui vise à suivre l’évolution d’une phase gazeuse initialement neutre au contact de la formation et de son eau porale grâce à un forage effectué et maintenu dans des conditions anaérobiques. Ces capteurs permettent un suivi quantitatif in situ et en ligne des gaz libérés par la formation à basse pression totale (<1,3 bar). Les modèles quantitatifs développés pour la mesure infrarouge ont une erreur relative moyenne de 1,66 % pour la pCO2 (mbar.m) et de 1,37 % pour la pCH4 (mbar.m). L’instrumentation IR d’un forage sur le site du Mt Terri et de deux forages sur le site de Bure (faciès C2b1 et C2d) a permis d’obtenir les courbes de transfert des deux gaz. Les courbes de transfert du CH4 ont été modélisées par un modèle de diffusion-advection qui ont permis l’évaluation de la concentration locale en CH4 dissous dans l’eau porale : elles sont comprises entre 3,06 et 14,23 mg.L-1 pour les AOP, et entre 0,36 et 1,28 mg.L-1 pour le faciès C2d et entre 0,56 et 1,55 mg.L-1 pour le faciès C2b1 des argilites de Bure. On montre que les équilibres eau/gaz/roche gouvernent la pCO2 après forage alors que la diffusion/advection explique son évolution sur le long terme. Une origine intraformationnelle des alcanes dissous est envisagée / An infrared sensor (IRTF) and an innovative Raman optical bench were implemented and developed in underground laboratories to improve our knowledge about migration mechanisms of dissolved gases (CO2 and CH4). This study is focussed on the characterisation of the initial state of the porewater of Callovo-Oxfordian marl (Bure) and Opalinus Clay (Mt Terri Middle Jurassic). These sensors are integrated into experimental devices of gas-equilibration test developed by Andra (PAC) to follow the gaseous phase behaviour in contact with the rock formation through a borehole drilled and maintained in anaerobic conditions, and initially filled with pure argon. These in situ sensors allow, on line quantitative analysis of gases released by the rock formation at low bulk pressure (<1.3 bar). Quantitative models were developed to transform peak intensities in partial pressures of gas. They give mean absolute relative errors about 1.66 % for pCO2 (mbar.m) and 1.37 % for pCH4 (mbar.m). Three years of IR monitoring of one borehole on the site of Mt Terri and two boreholes on the site of Bure (facies C2b1 and C2d) have been led. CH4 transfer curves were modelled by diffusion-advection. CH4 concentration in porewater from non-perturbed rock formation is estimated from all the experiments: concentrations between 3.06 and 14.23 mg.L-1 was obtained for Opalinus Clay, between 0.36 and 1.28 mg.L-1 for C2d facies and between 0.56 and 1.55 mg.L-1 for C2b1 facies in Callovo-Oxfordian marls of Bure. Gas/rock/water balance governs pCO2 after drilling, whereas diffusion/advection laws explain CO2 long-term profiles. An intra-formational origin of the organic gases can be proposed

Les fibres optiques utilisées pour le transfert d’information présentent des pertes de signal pendant leur propagation. Ainsi, ces signaux ont besoin d’être régulièrement amplifiés. De nos jours, l’Amplification Raman, basée sur le principe de diffusion Raman stimulée, est une des techniques utilisées pour réaliser ces amplifications. Les nanoparticules de métaux nobles ont des propriétés optiques uniques provenant de l’oscillation collective des électrons lorsqu’elles interagissent avec une onde électromagnétique. Ces particules absorbent fortement le champ électromagnétique à une fréquence appelée fréquence de résonance de plasmon de surface. Ce travail de thèse concerne l’influence des nanoparticules métalliques sur l’amélioration de l’Amplification Raman. Il s’inscrit dans le cadre du projet ANR Fenoptic (2010-2012), réunissant l’entreprise Draka et plusieurs laboratoires français (ICB Dijon, CMCP Paris, LPCML Lyon), qui s’intéressent à l’intégration des nanoparticules de métaux nobles à l’intérieur des fibres optiques afin d’utiliser la résonance de plasmon de surface pour améliorer l’efficacité des amplificateurs optiques. Dans ce travail, différentes sources de nanoparticules métalliques ont été examinées (suspensions, couches, préformes de fibre optique). Les expériences ont porté sur la caractérisation (forme et position du plasmon) de nanoparticules de métaux nobles incluses en matrices vitreuses ainsi que sur des mesures de spectroscopie Raman au travers desquelles le phénomène de Diffusion Raman Exaltée de Surface (SERS) a particulièrement été étudié. Pour la première fois, nous avons mis en évidence l’exaltation du signal Raman d’une matrice vitreuse. / Signals in optical fibers used for the transfer of information are attenuated due to impurities, scattering, absorption… To compensate for these losses, several techniques were developed like Erbium Doped Fiber Amplifier (EDFA). An alternative to rare earth doped fiber amplifier is Raman Amplification, which results from stimulated Raman scattering. Noble metal nanoparticles have optical properties induced by the collective oscillation of their conduction electrons when they interact with an electromagnetic wave. These particles strongly absorb the electromagnetic field at a frequency called surface Plasmon resonance frequency. This work is mainly based on effects leading to the improvement of the Raman Amplification. The ANR project Fenoptic (2010-2012), gathering Draka and several French laboratories (ICB (Dijon), CMCP (Paris), LPCML (Lyon)) is interested in the integration of noble metal nanoparticles in optical fibers using properties of the surface Plasmon resonance to improve the efficiency of optical amplifiers. In this work, different kinds of samples (suspensions, layers, optical fiber performs) with metal nanoparticles were studied. The experiments were based on the characterization (form and position of the Plasmon band) of noble metal nanoparticles in amorphous matrix and Raman spectroscopy was used to study the Surface Enhanced Raman Spectroscopy (SERS) effect. For the first time, we found the Raman signal exaltation of an amorphous matrix.

The transformation of the vibrational spectrum of Cu2Zn(Sn1−xGex)S4 single crystals over the entire composition range (0 ≤ x ≤ 1) is studied experimentally by low-temperature Raman scattering and photoluminescence spectroscopies, as well as theoretically in the framework of density functional theory (DFT). It is shown that unlike “classic” mixed binary II–VI and III–V compounds, which are characterized by either one- or two-mode behavior of spectra transformation upon composition variation, the vibrational modes of the quaternary semiconductor Cu2Zn(Sn1−xGex)S4 exhibit both types of behavior within the same alloy system. DFT calculations reveal that the two-mode transformation is in fact observed for the vibrational modes, which possess a very small dispersion across the Brillouin zone, that is typical for a molecular crystal. These modes are due to the “breathing” motion of sulfur within GeS4 and SnS4 tetrahedra. The effects of structural (positional) disorder of mixed crystals are analyzed based on Raman scattering as well as photoluminescence results. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.