The congruent sublimation of ZnSe compound is the negative conditional factor to ZnSe crystal vapor growth in zinc-selenium system. By replacing the homogeneous reaction between Zn(g) and Se₂(g) with non-homogenenous one, we developed a modified chemical vapor transport (CVT) method to grow ZnSe single crystals directely from zinc and selenium with the assistant of NH₄Cl transport agent, which has been recognized as the cheapest and the simplest technology to achieve ZnSe single crystals. ZnSe crystal grown free in this zinc-selenium-NH₄Cl system looks like the platelets, exhibiting a interesting growth habit rather than ZnSe bulk crystal grown by traditional CVT methods. As-grown ZnSe plate-like crystals offer us an opportunity to understand the vapor-free-growth mechanism of ZnSe crystal in closed-space CVT system, which was urgent for the effective control of ZnSe growth. Furthermore, the vapor-free-growth habit, growth orientation, micromorphologies and nucleation of as-grown ZnSe crystal were investigated using atomic force microscopy (AFM), field emission scanning electron microscope (FE-SEM) and rotating orientation x-ray diffraction (RO-XRD). The shape, number density and constituent elements ratio of growth nuclei on two surface of ZnSe crystal-flake were watched and analyzed. The studied results indicated that ZnSe crystal has (111)A face with Φ =4.64° and (111)B face with Φ=3.13°, and Φ is the angle between the (111) vicinal surface normal axle and the microface normal axle. ZnSe crystal has a sphenoid shape or growth habit. The growth nuclei formed primarily on (111)A surface, while few nuclei was found on (111)B surface. The free-growth of ZnSe crystal in zinc-selenium-NH₄Cl system was governed by three-dimension nuclei-growth mechanism on (111)B face. 

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