2.6 Characterization of single-walled carbon nanotubes by raman  (Page 6/7)

Limitations of raman spectroscopy

Though Raman spectroscopy has provides an exceedingly important tool for characterization of SWNTs, however, it suffers from few serious limitations. One of the main limitations of Raman spectroscopy is that it does not provide any information about the extent of functionalization in the SWNTs. The presence of D-band indicates disorder, i.e. side wall distribution, however it cannot differentiate between the number of substituents and their distribution. Following are the two main limitations of Raman Spectroscopy:

Quantification of substituents

This can be illustrated by the following examples. Purified HiPco tubes may be fluorinated at 150 °C to give F-SWNTs with a C:F ratio of approximately 2.4:1. The Raman spectra (using 780 nm excitation) for F-SWNTs shows in addition to the tangential mode at ~1587 cm ^-1 an intense broad D (disorder) mode at ~ 1295 cm ^-1 consistent with the side wall functionalization. Irrespective of the arrangements of the fluorine substituents, thermolysis of F-SWNTs results in the loss of fluorine and the re-formation of unfunctionalized SWNTs alnog with their cleavage into shorter length tubes. As can be seen from [link] , the intensity of the D-band decreases as the thermolysis temperature increases. This is consistent with the loss of F-substituents. The G-band shows a concomitant sharpening and increase in intensity.

As discussed above, the presence of a significant D mode has been the primary method for determining the presence of sidewall functionalization. It has been commonly accepted that the relative intensity of the D mode versus the tangential G mode is a quantitative measure of level of substitution. However, as discussed below, the G:D ratio is also dependent on the distribution of substituents. Using Raman spectroscopy in combination with XPS analysis of F-SWNTs that have been subjected to thermolysis at different temperatures, a measure of the accuracy of Raman as a quantitative tool for determining substituent concentration can be obtained. As can be seen from [link] , there is essentially no change in the G:D band ratio despite a doubling amount of functional groups.Thus, at low levels of functionalization the use of Raman spectroscopy to quantify the presence of fluorine substituents is a clearly suspect.

On the basis of above data it can be concluded that Raman spectroscopy does not provide an accurate quantification of small differences at low levels of functionalization, whereas when a comparison between samples with high levels of functionalization or large differences in degree of functionalization is requires Raman spectroscopy provides a good quantification.

Number versus distribution

Fluorinated nanotubes may be readily functionalized by reaction with the appropriate amine in the presence of base according to the scheme shown in [link] .