Seeded crystal growth of the acentric organic nonlinear optical material methyl-p-hydroxybenzoate from the vapor phase

Using in situ differential interference contrast microscopy (DICM), growth morphology, structure, and step velocities of the vicinal hillocks on {110} and {111̅} faces of MHB crystal seeds growing from the vapor phase have been investigated over a supersaturation (σ) range of (0.2 < σ < 0.6). Under these conditions of supersaturation, a dislocation induced growth mechanism was identified. Ex situ atomic force microscopy (AFM) shows that some dislocation induced hillocks exhibit hollow cores. The general observations of the {110} and {111̅} surfaces reveal that these faces follow a classical mode of layer growth, continuous generation of new layers by dislocation outcrops, which subsequently bunch and spread to cover the entire facets. A tangential step velocity of the slow and fast sides of {110} and {111̅} growth hillocks show a linear dependence with supersaturation in the region of (0.2 < σ < 0.4). Analysis of this dependence leads to the respective growth parameters for the identified growth mechanism: the activation energies for the slow and fast step motion of a growth hillock (EaS and EaF) and the corresponding kinetic coefficients (βaS and βaF), for both faces. The growth from physical vapor transport (PVT) shows that for the title material, as with a number of other polar materials, solvent poisoning is not the cause of the highly differential growth rates and is an intrinsic feature of the crystal. The results suggest that in terms of the production of large single crystals of high perfection by PVT, the supersaturation range for dislocation growth should be between 0.2 and 0.4. These findings provide a foundation for the rational design of large MHB crystals that may find applications utilizing their high optoelectronic potential.