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We present an x-ray diffraction study on n-hexane in tubular silicon channelsof approximately 10 nm diameter both as a function of the filling fraction f ofthe channels and as a function of temperature. Upon cooling, confined n-hexanecrystallizes in a triclinic phase typical of the bulk crystalline state.However, the anisotropic spatial confinement leads to a preferred orientationof the confined crystallites, where the <001> crystallographic directioncoincides with the long axis of the channels. The magnitude of this preferredorientation increases with the filling fraction, which corroborates theassumption of a Bridgman-type crystallization process being responsible for thepeculiar crystalline texture. This growth process predicts for a channel-likeconfinement an alignment of the fastest crystallization direction parallel tothe long channel axis. It is expected to be increasingly effective with thelength of solidifying liquid parcels and thus with increasing f. In fact, thefastest solidification front is expected to sweep over the full siliconnanochannel for f=1, in agreement with our observation of a practically perfecttexture for entirely filled nanochannels.

Preferred orientation of n-hexane crystallized in silicon nanochannels: A combined x-ray diffraction and sorption isotherm study