8.3 Characterization of covalently functionalized single-walled  (Page 2/3)

X-ray photoelectron spectroscopy (xps)

XPS confirms the presence of different elements in functionalized SWNTs. This is useful for identification of heteroatom elements such as F and N, and then XPS can be used for quantification with simple substituent groups and used indirectly. Deconvolution of XPS is useful to study fine structures on SWNTs. However, the overlapping of binding energies in the spectrum complicates quantification.

Spectroscopy

Raman spectroscopy

Raman spectroscopy is very informative and important for characterizing functionalized SWNTs. The tangential G mode ( ca . 1550 – 1600 cm ^-1 ) is characteristic of sp ² carbons on the hexagonal graphene network. The D-band, so-called disorder mode (found at ca . 1295 cm ^-1 ) appears due to disruption of the hexagonal sp ² network of SWNTs. The D-band was largely used to characterize functionalized SWNTs and ensure functionalization is covalent and occurred at the sidewalls. However, the observation of D band in Raman can also be related to presence of defects such as vacancies, 5-7 pairs, or dopants. Thus, using Raman to provide evidence of covalent functionalization needs to be done with caution. In particular, the use of Raman spectroscopy for a determination of the degree of functionalization is not reliable.

It has been shown that quantification with Raman is complicated by the distribution of functional groups on the sidewall of SWNTs. For example, if fluorinated-SWNTs (F-SWNTs) are functionalized with thiol or thiophene terminated moieties, TGA shows that they have similar level of functionalization. However, their relative intensities of D:G in Raman spectrum are quite different. The use of sulfur substituents allow for gold nanoparticles with 5 nm in diameter to be attached as a “chemical marker” for direct imaging of the distribution of functional groups. AFM and STM suggest that the functional groups of thio-SWNTs are group together while the thiophene groups are widely distributed on the sidewall of SWNTs. Thus the difference is not due to significant difference in substituent concentration but on substituent distribution, while Raman shows different D:G ratio.

Infra red spectroscopy

IR spectroscopy is useful in characterizing functional groups bound to SWNTs. A variety of organic functional groups on sidewall of SWNTs have been identified by IR, such as COOH(R), -CH ₂ , -CH ₃ , -NH ₂ , -OH, etc. However, it is difficult to get direct functionalization information from IR spectroscopy. The C-F group has been identified by IR in F-SWNTs. However, C-C, C-N, C-O groups associated with the side-wall functionalization have not been observed in the appropriately functionalized SWNTs.

Uv/visible spectroscopy

UV/visible spectroscopy is maybe the most accessible technique that provides information about the electronic states of SWNTs, and hence functionalization. The absorption spectrum shows bands at ca . 1400 nm and 1800 nm for pristine SWNTs. A complete loss of such structure is observed after chemical alteration of SWNTs sidewalls. However, such information is not quantitative and also does not show what type of functional moiety is on the sidewall of SWNTs.