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GeSe2 crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. Ge4+ is bonded to four equivalent Se2- atoms to form corner-sharing GeSe4 tetrahedra. All Ge–Se bond lengths are 2.40 Å. Se2- is bonded in a water-like geometry to two equivalent Ge4+ atoms.
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The GeSe:GeI4 vapor crystal growth system was characterized mass spectroscopically. A steady-state Knudsen effusion technique was developed to simulate the equilibrium conditions at one end of a vapor transport ampoule. It was found that the previously neglected equilibrium GeSe2(s) = GeSe(v) + 1/2Se2(v) reduces the Se2(v) concentration to an extent that sublimation/condensation of GeSe becomes the dominant transport mechanism. At total pressures near 1 atm the concentration of an additional Ge-Se-I vapor species becomes comparable to that of GeSe(v).
Previous work on the mass transport rate of the GeSe-GeI4 system has been reevaluated using the mass spectrometric results of Buchan and Rosenberger (1987), and considering the presence of GeSe(s) and GeSe2(s) phases in the source material. The present transport rate study confirms the previously derived dominance of the sublimation of GeSe at lower pressures of GeI4, and of chemical vapor transport at higher pressures of GeI4. It is noted that experimentally observed flux anomalies are model-independent.