Atomic layer deposition of GeSe films using HGeCl3 and [(CH3)3Si]2Se with the discrete feeding method for the ovonic threshold switch

Abstract

The ovonic threshold switch (OTS) based on the voltage snapback of amorphous chalcogenides possesses several desirable characteristics: bidirectional switching, a controllable threshold voltage (V-th) and processability for three-dimensional stackable devices. Among the materials that can be used as OTS, GeSe has a strong glass-forming ability (similar to 350 degrees C crystallization temperature), with a simple binary composition. Described herein is a new method of depositing GeSe films through atomic layer deposition (ALD), using HGeCl(3)and [(CH3)(3)Si](2)Se as Ge and Se precursors, respectively. The stoichiometric GeSe thin films were formed through a ligand exchange reaction between the two precursor molecules, without the adoption of an additional reaction gas, at low substrate temperatures ranging from 70 degrees C-150 degrees C. The pseudo-saturation behavior required a long time of Ge precursor injection to achieve the saturation growth rate. This was due to the adverse influence of the physisorbed precursor and byproduct molecules on the efficient chemical adsorption reaction between the precursors and reaction sites. To overcome the slow saturation and excessive use of the Ge precursor, the discrete feeding method (DFM), where HGeCl3 is supplied multiple times consecutively with subdivided pulse times, was adopted. DFM led to the saturation of the GeSe growth rate at a much shorter total injection time of the Ge precursor, and improved the film density and oxidation resistance properties. The GeSe film grown via DFM exhibited a short OTS time of similar to 40 ns, a similar to 10(7)ON/OFF current ratio, and similar to 10(4)selectivity. The OTS behavior was consistent with the modified Poole-Frenkel mechanism in the OFF state. In contrast, the similar GeSe film grown through the conventional ALD showed a low density and high vulnerability to oxidation, which prevented the OTS performance. The ALD method of GeSe films introduced here will contribute to the fabrication of a three-dimensionally integrated memory as a selector device for preventing sneak current.