Raman spectroscopy of graphene, its derivatives and graphene-based heterostructures

  • Axel Eckmann

Student thesis: Phd


In less than a decade of research, graphene has earned a long list of superlatives to its name and is expected to have applications in various fields such as electronics, photonics, optoelectronics, materials, biology and chemistry. Graphene has also attracted a lot of attention because its properties can be engineered either via intrinsic changes or by modification of its environment. Raman spectroscopy has become an ideal characterization method to obtain qualitative and quantitative information on these changes. This thesis investigates the possibility to change, supplement and monitor the electonic and optical properties as well as the chemical reactivity of graphene. It is achieved by i) substrate effect, ii) introduction of defects in the structure of graphene and iii) the combination of graphene with other two- dimensional crystals such as hexagonal boron nitride (h-BN) and transition metal dichacolgenides.In particular, the experimental work presented here describes:I - The influence of the type of substrate on the Raman intensity of graphene. This work leads to the calculation of the Raman scattering efficiency of graphene after CaF2 is found to be a suitable substrate for this kind of study in contrast to Si/SiOx that strongly modulates the Raman intensities. The G peak scattering efficiency is found to be about 200 x 10-5 m-1 Sr-1 at 2.4 eV while that of the 2D peak is one order of magnitude higher, confirming the resonant nature of the 2D peak Raman scattering process.II - An attractive method to produce large (up to several hundreds of microns across) and high quality graphene by anodic bonding. This cheap, fast and solvent-free method also allows introduction of vacancy like defects in the samples in a relatively controllable way. III - The Raman signatures of several types of defect such as sp3 sites, vacancies and substitutional atoms. For low defect concentration (stage 1) the intensitiy ratio I(D)/I(D') is constant and is 13 for sp3 sites, 9 for substitutional atoms and 7 for vacancies. This signature is explained using the local activation model recently proposed to model the amorphization trajectory of graphene with containing vacancy-like defects.IV - Controlled modification of graphene through mild oxygen plasma. The influence of sp3 sites on monolayer and bilayer graphene's electrical properties are discussed. In the case of bilayer under controlled conditions, it is possible to modify only the top layer. This may lead to decoupling between the two layers, which could explain the good mobility measured for this system. The possiblity to use such system as a sensor is discussed. V - The characteristic Raman signature of aligned graphene/h-BN superlattices. The Raman spectrum shows strong changes in perfectly aligned superlattices, which could be attributed to the reconstruction of the Dirac spectrum.VI - A prototype photovoltaic cell made of a graphene and tungsten disulphide (WS2) heterostructure with an external quantum efficiency of about 30%. The beneficial combination of an excellent absorption in WS2 atomically thin films due to the presence of van Hove singularities and graphene used as a transparent, flexible and conductive electrode is demonstrated.
Date of Award31 Dec 2013
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorCinzia Casiraghi (Supervisor)


  • Photocurrent
  • Heterostructure
  • Defects
  • Raman spectroscopy
  • Graphene

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