Biomedical Engineering Reference
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the step height using these methods the surface can be masked with a
flexible polymer prior to polymer deposition. Following deposition the mask
can be peeled off and the step height measured. Alternatively a scratch can
be made on the deposited polymer surface. Although AFM is potentially
slightly more accurate, the experimental effort is higher than using profi-
lometry. Techniques such as ellipsometry and quartz crystal micro-
gravimetry could also be used to determine the thickness of the polymer;
however, prior knowledge such as the refractive index or density of the
polymer is required to use these techniques. 7,99,100 Interferometric reflect-
ance spectroscopy, UV-visible interferometry and XPS can also be used to
determine film thickness within limitations.
d n 3 r 4 n g | 7
10.2.2.3 Electrografting Gradients
Electrografting is very useful for generating surfaces of a wide variety of
functional groups through electrochemical attachment onto pSi. Electro-
chemical reactions of pSi to form Si-C bonds on pSi can be performed using
organohalides, alkynes or Grignard reagents. 191
Organohalides, most commonly bromides or iodides, react with pSi upon
electrochemical reduction to form Si-C bonds as summarised in
Figure 10.13. The lithium iodide (LiI) present in the reaction reduces the
organo halide to form a radical in the first step of the reaction. 192 This alkyl
radical then removes a H radical from the Si-H surface, thereby creating
Si radicals. 193 Subsequently, the Si radicals react with the alkyl radicals to
form a Si-C bond. This cathodic electrografting reaction is prone to surface
oxidation arising from moisture or oxygen in the environment and hence,
the reaction must take place under an inert atmosphere.
A wide variety of functional groups can be attached to pSi using
this method (summarised by Gurtner et al. 192 ) including: trifluoroacetyl-
amino, 126 ethyl ester, 126 pentyl acetate, 107 bipyridines 194 and hydrocarbon-
based molecules. 107,195 Some functional group terminated alkyl halides,
however, can react with the Si-H surface. These groups include phenol
groups, alcohols or terminal acids, and they compete with the Si-C bond
formation. 192 These unwanted side reactions could be overcome by using
an ester functional group, which can be later reduced to a terminal acid or
alcohol. 192 The stability of a pSi surface can be further improved by
methylating or 'end-capping' the unreacted Si-H functional groups with
.
Figure 10.13 Mechanism for the attachment of organic functional groups onto pSi
by the electrochemical reduction of organohalides.
Adapted from Gurtner et al. 192
 
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