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To obtain these images, we used a method described in (28) and (32) that uses electrical double layer repulsive forces to image the charge distribution of an adsorbed layer on the sample. The images of the outer layer of the reacting mesostructured film were obtained by immersing the imaging tip and substrate in the reacting mixture and, once sufficient time was allowed for thermal and mechanical equilibration, setting the imaging setpoint in the repulsive precontact region. In this way, the tip is held ∼1 nm above the reacting surface and the scanning motion of the AFM produces a topological map of charge density.
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After 10 hours of reaction, in situ AFM images are difficult to obtain because of the appreciable growth of mesostructured silica on the top surface of the AFM flow cell and cantilever spring. The presence and irregular nature of both of these films disturb the reflection of the laser light beam used to monitor spring deflection.
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We observed +18% strain in the film grown in the nonequilibrium condition, in the case where the solution is confined in a thin film geometry by a wrap. We found that the film grows about an order of magnitude faster in this condition. A striking feature of our data is that there is a large change in the Bragg peak position as these films dry that corresponds to large changes in the film lattice constant and strain. For example, the degree of hexagonal strain varies from +18% while wet to +2% a few hours after removal from solution, and finally -7% several days later when they are dry. In this process, the lateral spacings of the film increased by 2% upon drying and finally by 5% after a few days. This implies that the 25% change in a/b ratio of the film upon drying is largely due to a change in the vertical lattice spacings due to drying shrinkage in the normal direction.
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64
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This work was supported by the U.S. Army Research Office (grant DAAH04-95-1-0102) and MRSEC program of the NSF (DMR-940032). We thank D. M. Dabbs for useful discussions and help in the manuscript preparation and Digital Instruments for technical support.
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