Search

This study introduces the atomic layer deposition (ALD) of tin selenide thin films using Sn(N(CH3)2)4 and Se(Si(CH3)3)2 with NH3 co-injection. The co-injection of NH3 with Se(Si(CH3)3)2 is essential for film growth to convert the precursor into a more reactive form. The most critical feature of this specific ALD process is that the chemical composition (Sn/Se ratio) could be varied by changing the growth temperature, even for the given precursor injection conditions. The composition and morphology of the deposited films varied depending on the process temperature. Below 150 °C, a uniform SnSe2 thin film was deposited in an amorphous phase, maintaining the oxidation states of its precursors. Above 170 °C, the composition of the film changed to 1 : 1 stoichiometry due to the crystallization of SnSe and desorption of Se. A two-step growth sequence involving a low-temperature seed layer was devised for the high-temperature ALD of SnSe to improve surface roughness. [ABSTRACT FROM AUTHOR]

Abstract: The work presented here introduces a materials strategy that involves physically transferred, ultrathin layers of silicon dioxide (SiO2) thermally grown on silicon wafers and then coated with hafnium oxide (HfO2) by atomic layer deposition, as barriers that satisfy requirements for even the most challenging flexible electronic devices. Materials and physics aspects of hydrolysis and ionic transport associated with such bilayers define their performance and reliability characteristics. Systematic experimental studies and reactive diffusion modeling suggest that the HfO2 film, even with some density of pinholes, slows dissolution of the underlying SiO2 by orders of magnitude, independent of the concentration of ions in the surrounding biofluids. Accelerated tests that involve immersion in phosphate‐buffered saline solution at a pH of 7.4 and under a constant electrical bias demonstrate that this bilayer barrier can also obstruct the transport of ions that would otherwise cause drifts in the operation of the electronics. Theoretical drift–diffusion modeling defines the coupling of dissolution and ion diffusion, including their effects on device lifetime. Demonstrations of such barriers with passive and active components in thin, flexible electronic test structures highlight the potential advantages for wide applications in chronic biointegrated devices. [ABSTRACT FROM AUTHOR]

This study introduces the atomic layer deposition (ALD) of tin selenide thin films using Sn(N(CH 3 ) 2 ) 4 and Se(Si(CH 3 ) 3 ) 2 with NH 3 co-injection. The co-injection of NH 3 with Se(Si(CH 3 ) 3 ) 2 is essential for film growth to convert the precursor into a more reactive form. The most critical feature of this specific ALD process is that the chemical composition (Sn/Se ratio) could be varied by changing the growth temperature, even for the given precursor injection conditions. The composition and morphology of the deposited films varied depending on the process temperature. Below 150 °C, a uniform SnSe 2 thin film was deposited in an amorphous phase, maintaining the oxidation states of its precursors. Above 170 °C, the composition of the film changed to 1 : 1 stoichiometry due to the crystallization of SnSe and desorption of Se. A two-step growth sequence involving a low-temperature seed layer was devised for the high-temperature ALD of SnSe to improve surface roughness.

An ovonic threshold switch (OTS) based on amorphous chalcogenide materials possesses several desirable characteristics, including high selectivity and fast switching speed, enabling the fabrication of one selector-one resistor (1S-1R) crossbar array (CBA) for random access memory. Among the several chalcogenide materials, GeSe offers high selectivity and a strong glass-forming ability with environment-friendly, simple binary composition. In this report, the GeSe thin films were deposited via atomic layer deposition (ALD) using Ge(N(Si(CH 3 ) 3 ) 2 ) 2 and ((CH 3 ) 3 Si) 2 Se for its envisioned application in fabricating three-dimensional vertical-type phase-change memory. Highly conformal Ge x Se 1- x films were obtained at a substrate temperature ranging from 70 to 160 °C. The unique deposition mechanism that involves Ge intermediates provided a way to modulate the composition of the Ge-Se films from 5:5 to 7:3. Low threshold voltages ranging from 1.2 to 1.4 V were observed depending on the composition. A cycling endurance of more than 10 6 was achieved with the Ge 0.6 Se 0.4 composition with 10 4 half-bias nonlinearity. This work presents the foundations for the future development of vertical-type 1S-1R arrays when combined with the ALD technique for Ge 2 Sb 2 Te 5 phase-change materials.

The thin-film growth conditions in a plasma-enhanced atomic layer deposition for the (3.0-4.5) nm thick HfO 2 film were optimized to use the film as the resistive switching element in a neuromorphic circuit. The film was intended to be used as a feasible synapse with analog-type conductance-tuning capability. The 4.5 nm thick HfO 2 films on both conventional TiN and a new RuO 2 bottom electrode required the electroforming process for them to operate as a feasible resistive switching memory, which was the primary source of the undesirable characteristics as the synapse. Therefore, electroforming-free performance was necessary, which could be accomplished by thinning the HfO 2 film down to 3.0 nm. However, the device with only the RuO 2 bottom electrode offered the desired functionality without involving too high leakage or shorting problems, which are due to the recovery of the stoichiometric composition of the HfO 2 near the RuO 2 layer. In conjunction with the Ta top electrode, which provided the necessary oxygen vacancies to the HfO 2 layer, and the high functionality of the RuO 2 as the scavenger of excessive incorporated oxygen vacancies, which appeared to be inevitable during the repeated switching operation, the Ta/3.0 nm HfO 2 /RuO 2 provided a highly useful synaptic device component in the neuromorphic hardware system.

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 (∼350 °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 [(CH 3 ) 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 °C-150 °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 HGeCl 3 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 ∼40 ns, a ∼10 7 ON/OFF current ratio, and ∼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.

The atomic layer deposition (ALD) of multication oxide films is complicated because the deposition behaviors of the component oxides are not independent of one another. In this study, the Ti and Sr atom incorporation behaviors during the ALD of SrTiO 3 films were quantitatively examined via the carefully designed ALD process sequences. H 2 O and O 3 were adopted as the oxygen sources of the SrO subcycles, whereas only O 3 was used for the TiO 2 ALD subcycles. Apart from the general conjecture on the roles of the different types of oxygen sources, the oxygen source that was adopted for the subcycles of the other component oxide had almost complete control of the metal atom incorporation behaviors. This means that the first half-cycle of ALD played a dominant role in determining the metal incorporation rate, which revealed the critical role of the steric hindrance effect during the metal precursor injection for the ALD rate. O 3 had almost doubled its reactivity toward the Ti and Sr precursors compared with H 2 O. Although these are the expected results from the common knowledge on ALD, the quantitative analysis of the incorporation behaviors of each metal atom provided insightful viewpoints for the ALD process of this technically important oxide material. Furthermore, the SrTiO 3 films with a bulk dielectric constant as high as 236 were obtained by the Ru-SrTiO 3 -RuO 2 capacitor structure.