Fazl Fatih Melemez Spring 2011 Homework 4,MAT 571 Introduction to Electron Microscopy

Physical Review B, Vol.47, Nu.11,15 March 1993

Electron Energy Loss Spectroscopy of Carbon nanometer-size tubes

P.M. AJAYAN, S. IIJIMA, T. ICHIHASHI

Aim of the Study; Making a detailed comparison of carbon nanotubes with regular graphite by using EELS to have better understanding for electron interactions of nano sized carbon structures. Solution Method and Procedure ; It is prepared that 5 different sized carbon nanotubes and a graphite specimen. Comparison of EELS datas give a close look for electron interactions of carbon materials. Carbon nanotubes are prepared with regular nanotube preparation method which is sonication with Ethanol solution. Sonication time is determining the nanotube diameter and of course number of the layers. It is used something called as holey carbon grid to put drops from the CNT solution on it to examine under TEM. Experimental details are given as following;
Operating voltage:200kV,Energy Resolution;2eV,data collection angle;10mrad(0.570deg), data acquisition time;1 min to not cause beam-induced-damage,electron probe;8-25 nm.

It is found that EELS from individual CNTs show change in the characteristic energy losspeaks as a function of tube size(layer number). In the Figure1, from -a- to eshow increasing layer numbered CNTs and f represents graphite sample. HRTEM images of CNTs are shown in Figure2.It is shown as in the fig. to help distinguish the peaks from each other since y axis has arbitrary units. First thing we can comment that EELS spectroscopy of carbon nanotubes has less background relatively to graphite layers if we plot them top of each other. The reason for this can be length of the electron path in the thickness direction. Another reason can be this, CNTs have electronically more strong and stable dipole moments and this might be caused that probability of transitions of electrons is lower in CNTs.

Fig2. Shows the wall thickness of CNT specimens. Study showed that plasmon-loss peaks depend on the tube wall thickness. We can see the gradual increasing from a to e specimen on plasmon loss from Fig1. Also plasmons in graphite show two prominent characteristic behaviors. One is at 7eV from one of the pi valence electrons (referring to p electrons) which is known as weaker than the sigma bonds. Other behavior is formed at 27 eV through remaining pi electron and collective oscillations of sigma electrons. When we look at the figure 1, we can see that CNTs loss peaks have broader energy range. The reason for this is put forward as this is because of the orientation -related energy-loss spectroscopy of cylindrical CNTs. When the beam starts from central position of the nanotube to the edges, spectrum is changing upon the curvature of the cylindrical structure and gives spectrum like this. Figure 3 is composed of loss peaks from glassy carbon and graphitic carbon.

As seen in the figure3, in the graphitic carbon(hexagonal structure with ordered c planes), contribution from the pi electrons to low plasmon losses is more visible than the one in glassy carbon. In other words, we can say that when the structure is less ordered along c direction, contribution from the pi electrons to the Plasmon losses is being less, thus energy loss is decreasing. Arrows in the Fig. 3 and secondary peak energy level around is less in glassy carbon (~20eV) through that reason.

In Figure4, a and b lines represent the CNTs with 12 layers(10 nm thickness) and 25 layers(20 nm thickness) respectively, and c for graphitic region. Arrows are showing the K shell excitations from and orbitals. First peak around 285 eV is and other is in range of 290-305 eV. This is because of the same reason which we mentioned in the first graph. Contibution to energy loss from orbital is less than orbital since it is known as having weaker bond strength.