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The formation of an SRG involves massive material motion It has been suggested that the process is in some way a surface phenomenon since nonazo capping layers tend to inhibit the phenomenon (Viswanathan et al, 1998) Many other experiments, however, con rm that azos deeper in the lm (which still absorb light) contribute to the mass transport (Yager and Barrett, 2007; Geue et al, 2002c) It is clear that the azobenzene isomerization is necessary to permit bulk material ow well below the polymer Tg It is often postulated that repeated trans-cis-trans cycles photosoften or photoplasticize the polymer matrix, enhancing polymer mobility by orders of magnitude While compelling, this explanation has been dif cult to directly observe Clearly motion is enabled during isomerization, as demonstrated by mass transport, increases in gas permeability (Kameda et al.

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380 migration control this transport when the electric field in the film is not very strong. If the electrochemical potential of an ion in the film in the steady state decreases with increasing distance from the surface of the electrode, then the current passing through the film (cf. Eq. 2.5.23) is given as (5.8.20) where \ix is the electrochemical potential of the ion at the film-electrolyte interface, JU2 is the value at the metal-film interface and / is the thickness of the film. If the film is insoluble then

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Java Data Matrix Barcode Generator . Data Matrix is also known as Data Matrix , ECC200. Compatibility: Barcode for Java library is compatible with the latest Data Matrix ISO specification [ISO/IEC 16022 (Second edition 2006-09-15)]. ... ASCII (1): it is used to encode data that mainly contains ASCII characters (0-127).

, 2003), the segregation of some material components to the free surface (Sharma et al, 2002), and the ability to optically erase SRGs (Lagugne-Labarthet et al, 2002; Sanchez et al, 2000; Jiang et al, 1998) The fact that incoherent illumination during SRG inscription enhances grating formation may also be interpreted as evidence that photosoftening is a dominant requirement for mass transport (Yang et al, 2004) Numerous reports have con rmed a reduction in the viscosity of polymer solutions on trans to cis conversion (Moniruzzaman et al, 2004; Bhatnagar et al, 1995; Kumar et al, 1984) This photothinning can be attributed to both chain conformation (reduced hydrodynamic size) and interchain interactions The extent to which such results can be extended into bulk lms is debatable.

(5.8.21)

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It is also worth noting that a depression of Tg near the surface of a polymer lm is now well established (Forrest and Dalnoki-Veress, 2001) One might be tempted to explain the mass transport by suggesting that an ultrathin layer of polymer material at the surface is suf ciently mobile (below Tg) to move, thereby exposing fresh surface, which then becomes mobile However, the Tg depressions typically measured are not suf cient to account for the process (especially in high Tg samples) Moreover, this does not explain why the mass patterning is only observed in samples that contain azobenzene..

Solution of the differential equation obtained by combining Eqs (5.8.20) and (5.8.21) yields the Wagner parabolic law of film growth, I2 = kt (5.8.22)

Despite compelling indirect experiments, there are few results that directly suggest photosoftening in bulk samples. Initial hints from AFM response (Kumar et al., 1998), experiments with a quartz crystal microbalance (Srikhirin et al., 2000), and electromechanical spectroscopy (Mechau et al., 2005, 2002; Srikhirin et al., 2000) all indicated that photosoftening occurred. However, the magnitude of the effect was found to be quite small (o10% change in modulus). Recent AFM modulus (Yager and Barrett, 2006b; Stiller et al., 2004) and tracer diffusion (Mechau et al., 2006) experiments have established that the softening is very small and certainly much smaller than the change in mechanical response that occurs upon heating a polymer to Tg. Thus, although mobility appears to be comparable to a polymer above Tg, other mechanical properties are only slightly modi ed. It may indeed be that isomerization merely enables localized molecular motion, but that the continual creation of molecular free volume pockets, which are then reoccupied by neighboring isomerizing chromophores, enables a net cooperative movement of material, akin to the displacement of a vacancy defect in a crystal or hole in a semiconductor (Mechau et al., 2002).

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