This paper introduces a new atomic layer deposition process for highly conformal, nanocrystalline-as-deposited GeTe–Sb2Te3 pseudobinary film growth at a deposition temperature of 130 °C. The process utilizes Ge(II)-amidoguanidinate (GeIIN(CH3)2[(N i Pr)2CN(CH3)2]), Te(Si(CH3)3)2, and Sb(OC2H5)3 with an NH3 coreagent. The alternative GeTe and Sb2Te3 subcycles produced various film compositions, all consistent with the GeTe–Sb2Te3 tie lines, owing to the stoichiometric reactions between the precursors without involvement of undesirable side reactions. The density of the nanocrystalline Ge2Sb2Te5 (GST225) films was 6.2 g·cm–3, similar to the density of the bulk crystalline material. The crystallization behaviors indicated that the distribution of the constituent elements of the GST225 films was highly uniform at the atomic level, as opposed to the case of the low-temperature (100 °C)-deposited films. The cubic to hexagonal transition at 350 °C upon postannealing produced (0001) hexagonal planes highly aligned along the substrate. The demonstration of the phase change memory device achieved high cycling endurance (>107). Considering that further scaling and optimization of the cell design can improve the electrical performance, the nanocrystalline GST films introduced herein can provide potential utilities in the large-capacity three-dimensional vertical-type phase change memory.
Atomic layer deposition (ALD) of phase-change materials has been suggested as the most feasible technique for the construction of high-aspect-ratio architectures required for ultrahigh-density phase-change random access memory (PcRAM). The recent advances in the ALD technique have established the foundations for the formation of conformal Ge–Te or Ge–Sb–Te films, but their electrical performance as a phase-change memory device has been rarely reported, especially with prolonged cycles. This study introduced Ge(II)–amido guanidinate (Ge(guan)NMe2 (guan = ( i PrN)2CNMe2, Me = CH3)) as a new ALD Ge precursor that was compatible with the high ALD temperature of up to 170 °C, which was necessary for achieving the high-density and stoichiometric as-deposited GeTe thin films. The films were deposited in an amorphous state. Coinjection of NH3 gas with the Te precursor (Te(SiMe3)2) was essential to initiate the feasible ALD reaction with the new Ge(II) precursor. Ab initio calculation proposed plausible exergonic chemical reaction pathways where NH3 actively participated in the dissociation of both −SiMe3 and guanidinate ligands from Te and Ge precursors, respectively. The ALD process showed self-limiting growth behavior and produced highly uniform and conformal morphologies. Low impurity levels (<5%) and a low crystallization temperature (180 °C) were observed for the samples deposited at 170 °C. The prototypical memory device showed a current–voltage curve with a voltage snapback region followed by switching to a low resistance state. Over 104 cycling endurance was achieved for the 170 °C grown GeTe film, whereas inferior endurance (<103) was observed for the low-temperature-grown GeTe.
Recent advances in nanoscale resistive memory devices offer promising opportunities for in-memory computing with their capability of simultaneous information storage and processing. The relationship between current and memory conductance can be utilized to perform matrix-vector multiplication for data-intensive tasks, such as training and inference in machine learning and analysis of continuous data stream. This work implements a mapping algorithm of memory conductance for matrix-vector multiplication using a realistic crossbar model with finite cell-to-cell resistance. An iterative simulation calculates the matrix-specific local junction voltages at each crosspoint, and systematically compensates the voltage drop by multiplying the memory conductance with the ratio between the applied and real junction potential. The calibration factors depend both on the location of the crosspoints and the matrix structure. This modification enabled the compression of Electrocardiographic signals, which was not possible with uncalibrated conductance. The results suggest potential utilities of the calibration scheme in the processing of data generated from mobile sensing or communication devices that requires energy/areal efficiencies.
In this paper, a new atomic layer deposition (ALD) process for depositing binary GeTe and ternary Ge–Sb–Te thin films is reported, where HGeCl3 and ((CH3)3Si)2Te were used as Ge and Te precursors, respectively. The precursors reacted together to form the films at a low substrate temperature of 50–100 °C, without involving any additional reactive process gas. HCl elimination from the Ge precursor to form the divalent Ge intermediate, GeCl2, is proposed to explain the formation of 1:1 composition stoichiometric GeTe films. The GeTe films are promising for use in phase change memory applications. Ternary Ge–Sb–Te films were deposited by combining the GeTe ALD process with a previously developed ALD process for Sb2Te3 films, where Sb(OC2H5)3 and ((CH3)3Si)2Te were employed respectively as the Sb and Te precursors. However, the composition of the ternary GeSbTe films deviated slightly from the desired GeTe–Sb2Te3 pseudobinary composition suggesting that a certain unwanted reaction was involved between the previously grown layer and incoming precursor molecules. Study of the mechanism revealed that reaction between the Ge precursor and the previously deposited Sb–Te layer caused a substantial portion of Sb to be removed from the Sb–Te layer as volatile SbCl3.
Ge–Sb–Se–Te quaternary films were prepared through atomic layer deposition (ALD) for ovonic threshold switching (OTS) applications.
The ovonic threshold switch (OTS) based on the voltage snapback of amorphous chalcogenides possesses several desirable characteristics: bidirectional switching, a controllable threshold voltage (V ) 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 and [(CH)Si]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 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 ON/OFF current ratio, and ∼10 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.
Chalcogenide materials have been regarded as strong candidates for both resistor and selector elements in passive crossbar arrays owing to their dual capabilities of undergoing threshold and resistance switching. This work describes the bipolar resistive switching (BRS) of amorphous GeSe thin films, which used to show Ovonic threshold switching (OTS) behavior. The behavior of this new functionality of the material follows filament-based resistance switching when Ti and TiN are adopted as the top and bottom electrodes, respectively. The detailed analysis revealed that the high chemical affinity of Ti to Se produces a Se-deficient Ge x Se1–x matrix and the interfacial Ti–Se layer. Electroforming-free BRS behavior with reliable retention and cycling endurance was achieved. The performance improvement was attributed to the Ti–Se interfacial layer, which stabilizes the composition of GeSe during the electrical switching cycles by preventing further massive Se migration to the top electrode. The conduction mechanism analysis denotes that the resistance switching originates from the formation and rupture of the high-conductance semiconducting Ge-rich Ge x Se1–x filament. The high-resistance state follows the modified Poole–Frenkel conduction.
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.
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