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Figure 11.17. Schematic illustration of the mechanism for the light-induced reorganization in self-assembled LC gels and the grating formation (LC host is not shown). Source: Zhao and Tong, 2003. Reprinted with permission.
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brous aggregates. How can UV irradiation increase the solubility of the aggregates of azo gelator in the LC host Even though the trans cis photoisomerization cannot be detected with the LC gel, presumably because of the extremely low concentration of azobenzene groups involved (only those on the surface of the 1% aggregates), it is believed that azobenzene group in the gelator is responsible. When the LC gel is heated to temperatures close to the melting of the aggregates, the gelator molecules on the surface would be mobile enough to undergo the trans cis photoisomerization. In other words, it is likely that the gelator molecules on the surface are converted from the trans to the cis isomer by light, which may increase the surface tension of the aggregates (Tong et al., 2005a,b; Ichimura et al., 2000) and, as a result, increase the dissolution of gelator molecules in the LC. It should be mentioned that with the use of a photomask on the side of the LC cell exposed to UV light, only gratings with a large period could be obtained. The commercially available cell used (from E.H.C, Japan) is made with two glass plates having a total thickness of B2250 mm. The probe light is diffracted when passing through the mask, and travels some 1125 mm before hitting the LC gel sample. This means that with masks having a period below 30 mm, the recording light actually irradiates the whole lm, and no grating can be formed. Gratings with smaller periods might be obtained using holographic recording. Kato and coworkers also achieved patterning with self-assembled LC gels (Moriyama et al., 2003). Using an azobenzene-containing gelator (structure in Fig. 11.18) and a low clearing temperature nematic LC, 4-cyano-4u-pentyl biphenyl (5CB), they demonstrated changes in LC gel states induced by the photoisomerization of azobenzene. As depicted in Fig. 11.18, a nematic gel is rst obtained; then it is exposed to UV light through a photomask for the trans cis photoisomerization. They found that the aggregates of gelator in the irradiated regions could be dissolved because of the solubility of azo gelator molecules in the
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O C (CH 2)10O N N CN
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(a) Writing UV light Photomask Nematic gel or Visible light (low power) Nematic LC gel Nematic LC gel Cholesteric LC gel Cholesteric LC phase (sol state) Fixing Keep at r.t. Storage
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Figure 11.18. (a) Schematic illustration of a patterning process with a selfassembled LC gel prepared using the shown azobenzene gelator. (b,c) Polarized optical micrographs of the self-assembled LC gel patterned by exposure to UV light through a photomask of 200-mm lattice and a photomask of 50-mm fringe spacing, respectively. Source: Moriyama et al., 2003. Adapted with permission.
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cis form. Being chiral, dissolved gelator molecules induce the formation of a cholesteric phase displaying the ngerprint texture in irradiated regions, while the nematic gel remains in nonirradiated areas. Upon removal of UV light, a slow cis trans backisomerization, either thermally activated or by low intensity visible light irradiation, results in the reaggregation of azo gelator molecules in the trans form. The aggregates grow along and stabilize the ngerprint structure, giving rise to a stable cholesteric gel in irradiated areas. Though no diffraction data were
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presented, different responses of nematic and cholesteric gels to electric eld may be explored for electrically tunable diffraction gratings.
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11.4.3. Electrical Switching
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In Fig. 11.16, the grating structure, for which electrical switching behavior was investigated, constitutes areas of almost pure cholesteric LC and areas of LC contained by brous aggregates of the azo gelator. LC molecules in the two areas respond to an electric eld differently, which makes the grating display electrically switchable diffraction ef ciency. For the measurements discussed later, an He Ne laser (633 nm) was used as the probe light, and the rst-order (+1) diffraction signal, Id, was measured using a high speed photodetector connected to a digital oscilloscope, whereas a high voltage waveform generator was used to apply the AC (1000 Hz), square wave, or pulse electric elds through the cell. Figure 11.19 shows the changes in the rst-order (+1) diffraction ef ciency as function of applied voltage for a grating obtained from the LC gel containing 1% gelator and 5% chiral dopant (period B40 mm). When the electric eld is applied for the rst time, that is, during the rst voltage increase, the diffraction ef ciency changes in an apparently complex fashion. It drops rst at B7 V and then rises at B16 V. To understand this behavior, it should be noted that after the grating is formed at 901C and cooled to room temperature, the cholesteric LC in the irradiated areas, where the aggregates are moved away by light, has a planar texture (Fig. 11.16d),
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Diffraction efficiency (%)