Understanding the Coexistence of Two Bipolar Resistive Switching Modes with Opposite Polarity in Pt/TiO2/Ti/Pt Nanosized ReRAM Devices.

Redox-type resistive random access memories based on transition-metal oxides are studied as adjustable two-terminal devices for integrated network applications beyond von Neumann computing. The prevailing, so-called, counter-eight-wise (c8w) polarity of the switching hysteresis in filamentary-type valence change mechanism devices originates from a temperature- and field-controlled drift-diffusion process of mobile ions, predominantly oxygen vacancies in the switching oxide. Recently, a bipolar resistive switching (BRS) process with opposite polarity, so-called, eight-wise (8w) switching, has been reported that, especially for TiO2 cells, is still not completely understood. Here, we report on nanosized (<0.01 µm2) asymmetric memristive cells from 3 to 6 nm thick TiO2 films by atomic layer deposition, which reveal a coexistence of c8w and 8w switching in the same cell. As important characteristics for the studied Pt/TiO2/Ti/Pt devices, the resistance states of both modes are nonvolatile and share one common state; i.e., the high-resistance state of the c8w mode equals the low-resistance state of the 8w-mode. A transition between the opposite hysteresis loops is possible by voltage control. Specifically, 8w BRS in the TiO2 cells is a self-limited low-energy nonvolatile switching process. Additionally, the 8w reset process enables the programming of multilevel high-resistance states. Combining the experimental results with data from simulation studies allows to propose a model, which explains 8w BRS by an oxygen transfer process across the Pt/TiO2 Schottky interface at the position of the c8w filament. Therefore, the coexistence of c8w and 8w BRS in the nanoscale asymmetric Pt/TiO2/Ti/Pt cells is understood from a competition between drift/diffusion of oxygen vacancies in the oxide layer and an oxygen exchange reaction across the Pt/TiO2 interface.

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

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 HGeCl3 and [(CH3)3Si]2Se 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 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 ∼40 ns, a ∼107 ON/OFF current ratio, and ∼104 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.

Nociceptive Memristor.

The biomimetic characteristics of the memristor as an electronic synapse and neuron have inspired the advent of new information technology in the neuromorphic computing. The application of the memristors can be extended to the artificial nerves on condition of the presence of electronic receptors which can transfer the external stimuli to the internal nerve system. In this work, nociceptor behaviors are demonstrated from the Pt/HfO2 /TiN memristor for the electronic receptors. The device shows four specific nociceptive behaviors; threshold, relaxation, allodynia, and hyperalgesia, according to the strength, duration, and repetition rate of the external stimuli. Such nociceptive behaviors are attributed to the electron trapping/detrapping to/from the traps in the HfO2 layer, where the depth of trap energy level is ≈0.7 eV. Also, the built-in potential by the work function mismatch between the Pt and TiN electrodes induces time-dependent relaxation of trapped electrons, providing the appropriate relaxation behavior. The relaxation time can take from several milliseconds to tens of seconds, which corresponds to the time span of the decay of biosignal. The material-wise evaluation of the electronic nociceptor in comparison with other material, which did not show the desired functionality, Pt/Ti/HfO2 /TiN, reveals the importance of careful material design and fabrication.

Structural Analyses of Phase Stability in Amorphous and Partially Crystallized Ge-Rich GeTe Films Prepared by Atomic Layer Deposition.

The local bonding structures of GexTe1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH3)3)2)2 and ((CH3)3Si)2Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.

Uniform Self-rectifying Resistive Switching Behavior via Preformed Conducting Paths in a Vertical-type Ta2O5/HfO2-x Structure with a Sub-µm(2) Cell Area.

To replace or succeed the present NAND flash memory, resistive switching random access memory (ReRAM) should be implemented in the vertical-type crossbar array configuration. The ReRAM cell must have a highly reproducible resistive switching (RS) performance and an electroforming-free, self-rectifying, low-power-consumption, multilevel-switching, and easy fabrication process with a deep sub-µm(2) cell area. In this work, a Pt/Ta2O5/HfO2-x/TiN RS memory cell fabricated in the form of a vertical-type structure was presented as a feasible contender to meet the above requirements. While the fundamental RS characteristics of this material based on the electron trapping/detrapping mechanisms have been reported elsewhere, the influence of the cell scaling size to 0.34 µm(2) on the RS performance by adopting the vertical integration scheme was carefully examined in this work. The smaller cell area provided much better switching uniformity while all the other benefits of this specific material system were preserved. Using the overstressing technique, the nature of RS through the localized conducting path was further examined, which elucidated the fundamental difference between the present material system and the general ionic-motion-related bipolar RS mechanism.

Resistance switching behavior of atomic layer deposited SrTiO3 film through possible formation of Sr2Ti6O13 or Sr1Ti11O20 phases.

Identification of microstructural evolution of nanoscale conducting phase, such as conducting filament (CF), in many resistance switching (RS) devices is a crucial factor to unambiguously understand the electrical behaviours of the RS-based electronic devices. Among the diverse RS material systems, oxide-based redox system comprises the major category of these intriguing electronic devices, where the local, along both lateral and vertical directions of thin films, changes in oxygen chemistry has been suggested to be the main RS mechanism. However, there are systems which involve distinctive crystallographic phases as CF; the Magnéli phase in TiO2 is one of the very well-known examples. The current research reports the possible presence of distinctive local conducting phase in atomic layer deposited SrTiO3 RS thin film. The conducting phase was identified through extensive transmission electron microscopy studies, which indicated that oxygen-deficient Sr2Ti6O13 or Sr1Ti11O20 phase was presumably present mainly along the grain boundaries of SrTiO3 after the unipolar set switching in Pt/TiN/SrTiO3/Pt structure. A detailed electrical characterization revealed that the samples showed typical bipolar and complementary RS after the memory cell was unipolar reset.

Giant Dielectric Permittivity in Ferroelectric Thin Films: Domain Wall Ping Pong.

The dielectric permittivity in ferroelectric thin films is generally orders of magnitude smaller than in their bulk. Here, we discover a way of increasing dielectric constants in ferroelectric thin films by ca. 500% by synchronizing the pulsed switching fields with the intrinsic switching time (nucleation of domain plus forward growth from cathode to anode). In a 170-nm lead zirconate titanate thin film with an average grain size of 850 nm this produces a dielectric constant of 8200 with the maximum nucleus density of 3.8 µm(-2), which is one to three orders of magnitude higher than in other dielectric thin films. This permits smaller capacitors in memory devices and is a step forward in making ferroelectric domain-engineered nano-electronics.

Electronic resistance switching in the Al/TiO(x)/Al structure for forming-free and area-scalable memory.

Electronic bipolar resistance switching (eBRS) in an Al/TiOx/Al structure, where the TiOx layer was reactively sputter-deposited, was examined in conjunction with a structural analysis using transmission electron microscopy. A thin (3-5 nm) insulating Al(Ti)Ox layer was formed at the bottom Al electrode interface, which provided the necessary asymmetric potential barrier for the eBRS to emerge, whereas the top Al electrode interface appeared to have provided the fluent carrier (electron) injection. The set and reset switching were related to the trapping and detrapping of the carriers at the trap centers, the characteristic energy of which was ∼0.86 eV, across the entire electrode area. The general features of this material system as the feasible RS memory were insufficient: endurance cycle, <∼8000, and retention time at 85 °C, 10(6) s. However, the detailed analysis of the switching behavior based on the space-charge limited current conduction mechanism, and its variation with the switching cycles, provided useful information on the general features of the eBRS, which could also be applicable to other binary (or even ternary) metal-oxide RS systems based on the electronic switching mechanism.

Bipolar resistive switching behavior of an amorphous Ge2Sb2Te5 thin films with a Te layer.

The mechanism of bipolar resistive switching (BRS) of amorphous Ge2Sb2Te5 (GST) thin films sandwiched between inert electrodes (Ti and Pt) was examined. Typical bipolar resistive switching behavior with a high resistance ratio (∼10(3)) and reliable switching characteristics was achieved. High-resolution transmission electron microscopy revealed the presence of a conductive Te-filament bridging between the top and bottom electrodes through an amorphous GST matrix. The conduction mechanism analysis showed that the low-resistance state was semiconducting and dominated by band transport, whereas Poole-Frenkel conduction governed the carrier transport in the high-resistance state. Thus, the BRS behavior can be attributed to the formation and rupture of the semiconducting conductive Te bridge through the migration of the Te ions in the amorphous GST matrix under a high electric field. The Te ions are provided by the thin (∼5 nm) Te-rich layer formed at the bottom electrode interface.

Evaluating the top electrode material for achieving an equivalent oxide thickness smaller than 0.4 nm from an Al-doped TiO2 film.

The effects of Pt and RuO2 top electrodes on the electrical properties of capacitors with Al-doped TiO2 (ATO) films grown on the RuO2 bottom electrode by an atomic layer deposition method were examined. The rutile phase ATO films with high bulk dielectric constant (>80) were well-grown because of the local epitaxial relationship with the rutile structured RuO2 bottom electrode. However, the interface between top electrode and ATO was damaged during the sputtering process of the top electrode, resulting in the decrease in the dielectric constant. Postmetallization annealing at 400 °C was performed to mitigate the sputtering damage. During the postmetallization annealing, the ATO layer near the RuO2 top electrode/ATO interface was well-crystallized because of the structural compatibility between RuO2 and rutile ATO, while the ATO layer near the Pt top electrode/ATO interface still exhibited an amorphous-like structure. Despite the same thickness of the ATO films, therefore, the capacitors with RuO2 top electrodes showed higher capacitance compared to the capacitors with Pt top electrodes. Eventually, an extremely low equivalent oxide thickness of 0.37 nm with low enough leakage current density (<1 × 10(-7) A/cm(2) at 0.8 V) and physical thickness of 8.7 nm for the next-generation dynamic random access memory was achieved from ATO films with RuO2 top electrodes.