Atomic Layer Deposition Process Research Articles

Room temperature atomic layer deposition of zinc titanium oxide using sequential adsorption of dimethyl zinc and tetrakis(dimethylamino)titanium

Complex oxide films of TiO2 and ZnO are deposited by RT atomic layer deposition (ALD) with a sequential adsorption process. In this ALD, a Zn precursor of dimethyl zinc (DMZ) and a Ti precursor of tetrakis(dimethylamino)titanium (TDMAT) are used. In the sequential adsorption step, the DMZ saturation on the surface is followed by partial adsorption of TDMAT. It is assumed that the TDMAT molecule is adsorbed on the DMZ uncovered area. The mixed layer of DMZ and TDMAT is formed in the adsorption step, followed by being oxidized with the plasma-excited humidified Ar. All the ALD processes are performed at RT without any sample heating in the ALD chamber. The growth per cycle of the balanced Zn and Ti oxide deposition is recorded at 0.086 nm/cycle. The mixing ratio of Zn and Ti is controlled by the TDMAT exposure in the adsorption step. In this study, the reaction model and the related rate equations to calculate the mixing concentration ratio are proposed based on the in situ observation of the surface reaction by IR absorption spectroscopy.

Atomic-scale oxygen-vacancy engineering in Sub-2 nm thin Al2O3/MgO memristors

Ultrathin (sub-2 nm) Al2O3/MgO memristors were recently developed using an in vacuo atomic layer deposition (ALD) process that minimizes unintended defects and prevents undesirable leakage current. These memristors provide a unique platform that allows oxygen vacancies (VO) to be inserted into the memristor with atomic precision and study how this affects the formation and rupture of conductive filaments (CFs) during memristive switching. Herein, we present a systematic study on three sets of ultrathin Al2O3/MgO memristors with VO-doping via modular MgO atomic layer insertion into an otherwise pristine insulating Al2O3 atomic layer stack (ALS) using an in vacuo ALD. At a fixed memristor thickness of 17 Al2O3/MgO atomic layers (∼1.9 nm), the properties of the memristors were found to be affected by the number and stacking pattern of the MgO atomic layers in the Al2O3/MgO ALS. Importantly, the trend of reduced low-state resistance and the increasing appearance of multi-step switches with an increasing number of MgO atomic layers suggests a direct correlation between the dimension and dynamic evolution of the conducting filaments and the VO concentration and distribution. Understanding such a correlation is critical to an atomic-scale control of the switching behavior of ultrathin memristors.

Reaction mechanisms of α,ω-bifunctional molecules toward atomic layer deposition versus molecular layer deposition

Atomic layer deposition (ALD) and molecular layer deposition (MLD) are key techniques used to fabricate high-quality thin films. Organic α,ω-bifunctional precursors often exhibit different growth behaviors depending on the functional groups as well as the chain length of the molecular backbone, so that some organic precursors produce thin films of organic-inorganic hybrid materials, while others may deposit purely inorganic thin films without incorporation of the hydrocarbon moiety. In this study, we investigated the surface reaction mechanisms of α,ω-bifunctional molecules (X(CH2)nX, n = 2, 3, 4, 5, 6, and X = OH, SH, NH2) with diethylzinc toward MLD and ALD using density functional theory (DFT) calculations. It was found that the length of the aliphatic alkyl chain and the terminal functional groups of bifunctional organic precursors significantly influences their reactivity, resulting in the possibility toward removal or incorporation of the organic moiety in the product. Bifunctional reactants with longer alkyl backbones (n > 4) showed higher reactivity for removal of the hydrocarbon chain, facilitated by a ω-2 hydrogen transfer reaction. Furthermore, a reactivity trend of SH > OH > NH2 for removal of the hydrocarbon chains was observed. Our study provides in-depth theoretical insights into the adsorption reaction mechanisms occurring when bifunctional molecules are employed as organic reactants in ALD and MLD processes.

Analysis of ferroelectric properties of ALD-Hf0.5Zr0.5O2 thin films according to oxygen sources

Ferroelectric Hf0.5Zr0.5O2 (HZO) thin films are mostly deposited with a thickness of less than 10 nm by an atomic layer deposition (ALD) process. Since the oxygen source used in the ALD process affects the residues in the deposited HZO films, the choice of oxygen source can be one of the important factors to improve ferroelectricity. From this point of view, the ferroelectric properties of 10-nm-thick ALD-HZO films according to the oxygen source (O3, H2O, and D2O) were comprehensively analyzed in this study. Heavy water (deuterium water, D2O) was used as a tracer to pinpoint the origin of hydrogen that could be derived from unreacted metal precursors or unreacted hydroxyl groups. As a result, it was revealed that the decrease in ferroelectric polarization and increase in leakage current observed in the H2O- and D2O-based HZO capacitors compared to the O3-based HZO capacitor were due to the oxygen source. These results highlight the importance of using O3 as a hydrogen-free oxygen source in the ALD process to achieve better ferroelectricity.

Nanocavity-Mediated Purcell Enhancement of Er in TiO2 Thin Films Grown via Atomic Layer Deposition.

The use of trivalent erbium (Er3+), typically embedded as an atomic defect in the solid-state, has widespread adoption as a dopant in telecommunication devices and shows promise as a spin-based quantum memory for quantum communication. In particular, its natural telecom C-band optical transition and spin-photon interface make it an ideal candidate for integration into existing optical fiber networks without the need for quantum frequency conversion. However, successful scaling requires a host material with few intrinsic nuclear spins, compatibility with semiconductor foundry processes, and straightforward integration with silicon photonics. Here, we present Er-doped titanium dioxide (TiO2) thin film growth on silicon substrates using a foundry-scalable atomic layer deposition process with a wide range of doping controls over the Er concentration. Even though the as-grown films are amorphous after oxygen annealing, they exhibit relatively large crystalline grains, and the embedded Er ions exhibit the characteristic optical emission spectrum from anatase TiO2. Critically, this growth and annealing process maintains the low surface roughness required for nanophotonic integration. Finally, we interface Er ensembles with high quality factor Si nanophotonic cavities via evanescent coupling and demonstrate a large Purcell enhancement (≈300) of their optical lifetime. Our findings demonstrate a low-temperature, nondestructive, and substrate-independent process for integrating Er-doped materials with silicon photonics. At high doping densities this platform can enable integrated photonic components such as on-chip amplifiers and lasers, while dilute concentrations can realize single ion quantum memories.

Reliability Engineering of High‐Mobility IGZO Transistors via Gate Insulator Heterostructures Grown by Atomic Layer Deposition

AbstractThe reliability of oxide‐semiconductor (OS) thin‐film transistors (TFTs) is significantly influenced by the gate insulator (GI). During electrical bias stress, the defect sites near the semiconductor/GI interface and/or within the GI may trap electrons, which makes the threshold voltage (Vth) shift toward positive values. On the other hand, carbon (C) or hydrogen (H) atoms may diffuse from the GI into the active layer, and act as shallow donors, which induce negative Vth shifts (ΔVth). In this paper, an in situ atomic layer deposition (ALD)‐based GI heterostructure is introduced, which consists of a stack of two complementary materials, namely Al2O3 and SiO2. Here, a competition occurs between electron trapping in Al2O3 (positive ΔVth) and carrier generation from H atoms in SiO2 (negative ΔVth) which allows the achievement of nearly zero ΔVth under positive bias temperature stress (PBTS). This strategy is successfully applied to a high‐mobility (>50 cm2 Vs−1) ALD‐based indium‐gallium‐zinc oxide (IGZO) device, resulting in a net ∆Vth of −0.02 V under PBTS and drain current variation (∆ID) of +0.49% under constant current stress (CCS). The application of an in situ ALD process thus offers valuable insights to resolve the mobility versus reliability trade‐off in high‐performance oxide TFTs.

Study on the Sodium-Doped Titania Interface-Type Memristor.

Memristors integrated into a crossbar-array architecture (CAA) are promising candidates for analog in-memory computing accelerators. However, the relatively low reliability of the memristor device and sneak current issues in CAA remain the main obstacles. Alkali ion-based interface-type memristors are promising solutions for implementing highly reliable memristor devices and neuromorphic hardware. This interface-type device benefits from self-rectifying and forming-free resistive switching (RS), and exhibits relatively low variation from device to device and cycle to cycle. In a previous report, we introduced an in situ grown Na/TiO2 memristor using atomic layer deposition (ALD) and proposed a RS mechanism from experimentally measured Schottky barrier modulation. Self-rectifying RS characteristics were observed by the asymmetric distribution of Na dopants and oxygen vacancies as the Ti metal used as the adhesion layer for the bottom electrode diffuses over the Pt electrode at 250 °C during the ALD process and is doped into the TiO2 layer. Here, we theoretically verify the modulation of the Schottky barrier at the TiO2/Pt electrode interface by Na ions. This study fabricated a Pt/Na/TiO2/Pt memristor device and confirmed its self-rectifying RS characteristics and stable retention characteristics for 24 h at 85 °C. Additionally, this device exhibited relative standard deviations of 27 and 7% in the high and low resistance states, respectively, in terms of cycle-to-cycle variation. To verify the RS mechanism, we conducted density functional theory simulations to analyze the impact of Na cations at interstitial sites on the Schottky barrier. Our findings can contribute to both fundamental understanding and the design of high-performance memristor devices for neuromorphic computing.

Study of Mid-Pressure Ar Radiofrequency Plasma Used in Plasma-Enhanced Atomic Layer Deposition of α-Al2O3

This study investigated the characteristics of radiofrequency, middle-pressure argon plasma used in the atomic layer deposition (ALD) of Al2O3 films. Based on the electrical characteristics—the current, voltage, and phase shift between them—and the stability of the plasma plume, the optimum plasma power, allowing reliable switching on of the plasma for any step of an ALD cycle, was determined. Spectral measurements were performed to determine the gas temperature and reactive species that could be important in the ALD process. The density of metastable argon atoms was estimated using tunable laser absorption spectroscopy. It was concluded that plasma heating of substrates did not affect film growth. The crystallization-enhancing effect of plasma observed in these experiments was due to the action of OH radicals produced in the plasma.

Effect of Co-Reactants on Interfacial Oxidation in Atomic Layer Deposition of Oxides on Metal Surfaces.

We have examined the atomic layer deposition (ALD) of Al2O3 using TMA as the precursor and t-BuOH and H2O as the co-reactants, focusing on the effects of the latter on both the ALD process and the possible modification of the underlying substrate. We employed a quartz crystal microbalance (QCM) to monitor ALD in situ and in real time, and the deposited thin films have been characterized using X-ray photoelectron spectroscopy, spectroscopic ellipsometry, X-ray reflectivity, and atomic force microscopy. Growth of thin films of Al2O3 using TMA and either t-BuOH or H2O as the co-reactant at T = 285 °C produces thin films of similar physical properties (density, stoichiometry, minimal carbon incorporation), and the growth rate per cycle is similar for the two co-reactants at this temperature. At a lower temperature of T = 120 °C, the behavior is starkly different, where growth occurs with H2O but not with t-BuOH. At either process temperature, we find no evidence for significant coverages of a long-lived tert-butoxy species from the reaction of t-BuOH. Deposition of thin films of Al2O3 on metal surfaces of Cu and Co has been examined for evidence of interfacial oxidation. While growth with either co-reactant does not lead to the oxidation of the underlying Cu substrate, use of H2O leads to the oxidation of Co, but use of t-BuOH as the co-reactant does not. Thermodynamic factors may affect the early stages of growth, as Al species will likely scavenge all free O species. In contrast, at later times, diffusion of species through the deposited Al2O3 thin film could result in oxidation at the Al2O3|metal interface, a process that is strongly hindered in the case of t-BuOH due to its size. This observation highlights the importance of the choice of the co-reactant concerning ALD of oxides on metal surfaces.

Atomic layer deposition of two-dimensional layered zirconium sulfide

Zirconium disulfide (ZrS2) is a two-dimensional (2D) layered transition metal dichalcogenide (TMDC) and has important implications in optoelectronics and energy storage. Despite some research efforts reported to date for synthesizing 2D ZrS2, there still lacks a method to grow large-scale continuous ZrS2 thin films. In this study, we developed a low temperature vapor-phase process for controllably growing zirconium sulfide (ZrSx) films via atomic layer deposition (ALD), using tetrakis (dimethylamido)zirconium (TDMA-Zr) and H2S as the precursors in the range of 75–300 °C. We verified the self-limiting growth behavior of the ZrSx ALD using an in-situ quartz crystal microbalance (QCM). Furthermore, we characterized the resultant ZrSx films using a suite of instruments, including scanning electron microscopy (SEM), synchrotron X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM). The results showed that the growth per cycle (GPC) of the ZrSx films varies with temperature and decreases from ∼1.2 Å/cycle at 75 °C to ∼0.3 Å/cycle at 300 °C. The as-deposited films are mainly amorphous in all the temperatures and have an S/Zr ratio varying from ∼2 to 1. Very interestingly, our in situ annealing HR-TEM analyses revealed that the resultant films could transform from an amorphous layer into a layer of crystalline nanoparticles of 2D ZrS2 with increasing temperatures up to 1000 °C. We also confirmed that the as-deposited ZrSx films are electrochemically active and show promising capability as an anode material for lithium-ion batteries (LIBs). Thus, this study represents a new ALD process for ZrSx, which may have important applications in multiple areas.

Water Dose influence to the ALD hafnium oxide process: Simulation and experiment

In this work, we report a two-dimensional gas-dynamic model for the formation of hafnium oxide from TDMAH and water during the atomic layer deposition (ALD) process. Application of the model is demonstrated by the example of water cycle, in which the monolayer of functional groups –OH is formed. The simulation results show that the duration of the water pulse affects the dynamics of surface coverage with the -OH groups. At short pulse durations, the resulting coverage of the film surface with -OH groups becomes incomplete and has heterogeneous distribution over the film surface, which is due to the design of the reaction chamber and regimes of gas supply. The amount of residual water vapor depends on the duration of the water pulse and pumping regimes. Experimental data show the influence of water pulse duration on the refractive index, which is related to the structure of the deposited layer (composition, morphology, etc.). Based on experimental data and modeling results, we explain the effect of water pulse duration on the refractive index by the change in reaction mechanisms depending on water amount in the chamber. With a lack of water, the incomplete monolayer of –OH groups is formed and a {HfO2-y} layer grows as a result of the monomolecular decomposition of the precursor. With an excess of water, we expect the implementation of multilayer adsorption of water, provoking the reaction of the precursor in the volume of the water film, leading to the formation of the product {HfO2+y}.

Reducing contact resistance of MoS2-based field effect transistors through uniform interlayer insertion via atomic layer deposition.

Molybdenum disulfide (MoS2), a semiconducting two-dimensional layered transition metal dichalcogenide (2D TMDC), with attractive properties enables the opening of a new electronics era beyond Si. However, the notoriously high contact resistance (RC) regardless of the electrode metal has been a major challenge in the practical applications of MoS2-based electronics. Moreover, it is difficult to lower RC because the conventional doping technique is unsuitable for MoS2 due to its ultrathin nature. Therefore, the metal-insulator-semiconductor (MIS) architecture has been proposed as a method to fabricate a reliable and stable contact with low RC. Herein, we introduce a strategy to fabricate MIS contact based on atomic layer deposition (ALD) to dramatically reduce the RC of single-layer MoS2 field effect transistors (FETs). We utilize ALD Al2O3 as an interlayer for the MIS contact of bottom-gated MoS2 FETs. Based on the Langmuir isotherm, the uniformity of ALD Al2O3 films on MoS2 can be increased by modulating the precursor injection pressures even at low temperatures of 150 °C. We discovered, for the first time, that film uniformity critically affects RC without altering the film thickness. Additionally, we can add functionality to the uniform interlayer by adopting isopropyl alcohol (IPA) as an oxidant. Tunneling resistance across the MIS contact is lowered by n-type doping of MoS2 induced by IPA as the oxidant in the ALD process. Through a highly uniform interlayer combined with strong doping, the contact resistance is improved by more than two orders of magnitude compared to that of other MoS2 FETs fabricated in this study.

Scalable Large-Area 2D-MoS2/Silicon-Nanowire Heterostructures for Enhancing Energy Storage Applications.

Two-dimensional (2D) transition-metal dichalcogenides have shown great potential for energy storage applications owing to their interlayer spacing, large surface area-to-volume ratio, superior electrical properties, and chemical compatibility. Further, increasing the surface area of such materials can lead to enhanced electrical, chemical, and optical response for energy storage and generation applications. Vertical silicon nanowires (SiNWs), also known as black-Si, are an ideal substrate for 2D material growth to produce high surface-area heterostructures, owing to their ultrahigh aspect ratio. Achieving this using an industrially scalable method paves the way for next-generation energy storage devices, enabling them to enter commercialization. This work demonstrates large surface area, commercially scalable, hybrid MoS2/SiNW heterostructures, as confirmed by Raman spectroscopy, with high tunability of the MoS2 layers down to the monolayer scale and conformal MoS2 growth, parallel to the silicon nanowires, as verified by transmission electron microscopy (TEM). This has been achieved using a two-step atomic layer deposition (ALD) process, allowing MoS2 to be grown directly onto the silicon nanowires without any damage to the substrate. The ALD cycle number accurately defines the layer number from monolayer to bulk. Introducing an ALD alumina (Al2O3) interface at the MoS2/SiNW boundary results in enhanced MoS2 quality and uniformity, demonstrated by an order of magnitude reduction in the B/A exciton photoluminescence (PL) intensity ratio to 0.3 and a reduction of the corresponding layer number. This high-quality layered growth on alumina can be utilized in applications such as for interfacial layers in high-capacity batteries or for photocathodes for water splitting. The alumina-free 100 ALD cycle heterostructures demonstrated no diminishing quality effects, lending themselves well to applications that require direct electrical contact with silicon and benefit from more layers, such as electrodes for high-capacity ion batteries.

Unfolding an Elusive Area-Selective Deposition Process: Atomic Layer Deposition of TiO2 and TiON on SiN vs SiO2.

Area-selective atomic layer deposition (AS-ALD) processes for TiO2 and TiON on SiN as the growth area vs SiO2 as the nongrowth area are demonstrated on patterns created by state-of-the-art 300 mm semiconductor wafer fabrication. The processes consist of an in situ CF4/N2 plasma etching step that has the dual role of removing the SiN native oxide and passivating the SiO2 surface with fluorinated species, thus rendering the latter surface less reactive toward titanium tetrachloride (TiCl4) precursor. Additionally, (dimethylamino)trimethylsilane was employed as a small molecule inhibitor (SMI) to further enhance the selectivity. Virtually perfect selectivity was obtained when combining the deposition process with intermittent CF4/N2 plasma-based back-etching steps, as demonstrated by scanning and transmission electron microscopy inspections. Application-compatible thicknesses of ∼8 and ∼5 nm were obtained for thermal ALD of TiO2 and plasma ALD of TiON.

Impact of atomic layer deposition temperature on electrical and optical properties of ZnO:Al films

This work highlights the impact of growth temperature on the electrical and optical properties of Al-doped ZnO (AZO) films deposited by the atomic layer deposition (ALD) technique. The ALD process and super-cycle sequence have been optimized, identifying their influence on film resistivity. By using this optimum ALD procedure, the optical and electrical properties of AZO films have been widely analyzed considering the deposition temperature. Results show promising values with film resistivity in the range of 1 mΩcm and average optical absorption below 2% for 50 nm thick AZO layers. Hall effect, X-ray diffraction and ellipsometry measurements point out that these excellent values are related to their high carrier concentration and mobility, crystalline phase and optical band gap, resulting in ALD AZO films with excellent properties to be applied in photovoltaic devices as transparent conductive oxide electrode.

Formation of oxygen vacancy at surfaces of ZnO by trimethylaluminum

The two-dimensional electron gas (2DEG) is a group of electrons that can move freely in horizontal dimensions but are confined in the third direction. It has been reported that atomic layer deposition (ALD) of Al2O3 on various reducible n-type oxides can lead to the formation of 2DEG at the heterojunction interfaces, among which ZnO is known to provide promising properties. In this study, we have performed a theoretical analysis using density functional theory calculations combined with experimental investigations to elucidate the surface reactions of Al2O3 ALD on low-index nonpolar ZnO surfaces, specifically focusing on the formation of oxygen vacancies (VO). The trimethylaluminum precursor was observed to undergo sequential dissociation of CH3 ligands, leading to the removal of surface oxygen of ZnO in the form of dimethyl ether. In addition, by examining the electronic structure after the removal of oxygen, the localization of the charge density at the surface was confirmed. Experimentally, the carrier density of the 2DEG at the Al2O3/ZnO interface showed a strong dependence on the ALD process temperature of Al2O3, confirming the endothermic nature of the formation of the 2DEG. By examining the characteristics of the 2DEG induced by VO, insights into the fundamental comprehension of oxide-based 2DEG systems are provided.

Advanced TiO2/Al2O3 Bilayer ALD Coatings for Improved Lithium-Rich Layered Oxide Electrodes.

Surface modification is a highly effective strategy for addressing issues in lithium-rich layered oxide (LLO) cathodes, including phase transformation, particle cracking, oxygen gas release, and transition-metal ion dissolution. Existing single-/double-layer coating strategies face drawbacks such as poor component contact and complexity. Herein, we present the results of a low-temperature atomic layer deposition (ALD) process for creating a TiO2/Al2O3 bilayer on composite cathodes made of AS200 (Li1.08Ni0.34Co0.08Mn0.5O2). Electrochemical analysis demonstrates that TiO2/Al2O3-coated LLO electrodes exhibit improved discharge capacities and enhanced capacity retention compared with uncoated samples. The TAA-5/AS200 bilayer-coated electrode, in particular, demonstrates exceptional capacity retention (∼90.4%) and a specific discharge capacity of 146 mAh g-1 after 100 cycles at 1C within the voltage range of 2.2 to 4.6 V. The coated electrodes also show reduced voltage decay, lower surface film resistance, and improved interfacial charge transfer resistances, contributing to enhanced stability. The ALD-deposited TiO2/Al2O3 bilayer coatings exhibit promising potential for advancing the electrochemical performance of lithium-rich layered oxide cathodes in lithium-ion batteries.

Optimizing Atomic Layer Deposition Processes with Nanowire‐Assisted TEM Analysis

AbstractAtomic layer deposition (ALD) is one of the premier methods to synthesize ultra‐thin materials on complex surfaces. The technique allows for precise control of the thickness down to single atomic layers, while at the same time providing uniform coverage even for structures with extreme aspect ratios such as deep trenches or wires. While many materials can be readily deposited using ALD there is still a lot of research going on to make other materials more accessible. When establishing a new process or adapting an existing process to a new reactor, precise optimization of the deposition parameters is necessary. However, characterizing the parameters of deposition rate, uniformity, composition, and structure is a challenging and time‐consuming task. Here a method is presented to optimize these process parameters during ALD deposition using high‐aspect ratio nanowires and transmission electron microscopy (TEM). Nanowire samples are prepared directly on TEM grids that are put into the ALD reactor during deposition. Within min of the process the coated nanowires can be analyzed by TEM to obtain the thickness of the layers, chemical composition, crystallinity, and conformality of the coating. This allows for a high testing throughput and subsequently a rapid optimization of deposition parameters.

Investigation of atomic layer deposition methods of Al2O3 on n-GaN

In this work, three atomic layer deposition (ALD) approaches are used to deposit an Al2O3 gate insulator on n-GaN for application in vertical GaN power switches: thermal ALD (ThALD), plasma-enhanced ALD (PEALD), and their stacked combination. The latter is a novel method to yield the most ideal insulating layer. Also, the influence of an in situ NH3 or H2 plasma pre-treatment is studied. Planar MIS capacitors are used to investigate the electrical properties and robustness of the gate insulators. In vacuo x-ray photoelectron spectroscopy (XPS) is used to study the changes in chemical composition after every surface treatment. XPS shows that all plasma pre-treatments efficiently remove all carbon contamination from the surface, but only NH3 plasma is observed to additionally remove the native oxide from the n-GaN surface. The water precursor step in the ThALD process does not completely remove the CH3 ligands of the trimethylaluminum precursor step, which might electrically be associated with a reduced forward bias robustness. The O2 plasma step in the PEALD process is associated with the removal of carbon and a tremendous increase of the O content in the GaN surface region. Electrically, this strongly correlates to an enhanced forward bias robustness and an increased forward bias hysteresis, respectively. The ThALD/PEALD stack method mitigates the shortcomings of both ALD processes while maintaining its advantages. Electrical measurements indicate that the stack method alongside NH3 plasma pretreatment provides the best characteristics in terms of hysteresis, threshold voltage, forward bias robustness, and interface trap density of states.

High-Reliability and Self-Rectifying Alkali Ion Memristor through Bottom Electrode Design and Dopant Incorporation.

Ionic memristor devices are crucial for efficient artificial neural network computations in neuromorphic hardware. They excel in multi-bit implementation but face challenges like device reliability and sneak currents in crossbar array architecture (CAA). Interface-type ionic memristors offer low variation, self-rectification, and no forming process, making them suitable for CAA. However, they suffer from slow weight updates and poor retention and endurance. To address these issues, the study demonstrated an alkali ion self-rectifying memristor with an alkali metal reservoir formed by a bottom electrode design. By adopting Li metal as the adhesion layer of the bottom electrode, an alkali ion reservoir was formed at the bottom of the memristor layer by diffusion occurring during the atomic layer deposition process for the Na:TiO2 memristor layer. In addition, Al dopant was used to improve the retention characteristics by suppressing the diffusion of alkali cations. In the memristor device with optimized Al doping, retention characteristics of more than 20 h at 125 °C, endurance characteristics of more than 5.5 × 105, and high linearity/symmetry of weight update characteristics were achieved. In reliability tests on 100 randomly selected devices from a 32 × 32 CAA device, device-to-device and cycle-to-cycle variations showed low variation values within 81% and 8%, respectively.