The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples
is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified
by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as
a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an
acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of
benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of
photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently
modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a
unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films
and their operational functionality in thin film devices for future optoelectronic applications.
