Dimensional changes in electroactive films of nickel hydroxide, iridiu
m oxide and polyaniline were investigated in situ in the electrochemic
al environment by scanning tunneling microscopy (STM), atomic force mi
croscopy (AFM) and intermittent contact atomic force microscopy (ICAFM
) during electrochemical oxidation and reduction. The advantages and d
isadvantages of the three measuring techniques are demonstrated with s
pecific examples. While STM measurements are ambiguous due to the chan
ging conductance of the sample during the redox process, AFM measureme
nts on soft films such as anodic iridium oxide (AIROF) may result in s
urface modifications. Intermittent contact AFM (ICAFM) appears to be b
est suited for most samples. Shrinking of up to 40% could be observed
on nickel oxide films during oxidation, which depended upon the locati
on on the sample investigated and on the measuring technique employed.
For a polyaniline film with a reversible charge capacity of 4.3 mC/cm
(2) corresponding to 75 +/- 7 nm film thickness, a thickness increase
of 10 +/- 3 nm was observed during oxidation.