Applications In Memory Devices Research Articles

Similarities and differences in the ordering at short and long ranges in a NaNbO3 based Pb-free smart system: a key to functional properties

In this study, we have investigated the crystal structure of the solid solution of antiferroelectric NaNbO3(NN) with ferroelectric Ba0.9Ca0.1TiO3(BCT), i.e. (1−x)NN- xBCT for 0⩽x⩽1.0 using High-resolution powder x-ray diffraction (HR-XRD) data, dielectric measurements in conjunction with Raman spectroscopic studies. The investigation of long-range structural phase transitions as a function of composition(x) using x-ray diffraction is complemented by short-range structural insights from Raman spectroscopy. The incorporation of BCT disrupts the delicate antiferroelectric ordering of NN and stabilizes various ferroelectric phases with increasing BCT content(x). At x = 0.10, the simultaneous presence of two ferroelectric phases viz., Pmc21 and Amm2, results in a threefold rise in remanent polarization compared to off-boundary compositions. The composition with higher BCT content (i.e. x⩾0.50 ) has shown the anomalous existence of two long-range cubic structures, both of which are characterized by Pm 3¯ m space group. In spite of having a two-phase long-range centrosymmetric structure, we have observed a slim Polarization vs. Electric field(P-E) hysteresis loop for 0.50⩽x⩽0.80 . This contrapositive behavior (i.e. hysteresis loop in a centrosymmetric structure) has been attributed to the correlations among local static polar distortions of rhombohedral type ascertained using Raman spectroscopy. The coexistence of two ferroelectric phases at room temperature(for x = 0.10) and a slim hysteresis loop (for 0.50⩽x⩽0.80 ) make these compositions potential ingredients for applications in ferroelectric memory and energy storage devices.

(Invited) Near-Field Optics and Its Applications in Nanoscale Materials: A Review

In this paper, we first offer an overview of aperture-type scanning near field optical microscopy –a family of super-resolution imaging techniques based on evanescent waves, which can be combined with atomic force microscopy and are capable of subwavelength resolution nano-optical imaging. In the second part of this review, we will discuss a few applications in which our group capitalized on the super-resolution resolving power of SNOM to design specific nano-optical and nano-photonic systems for light harvesting, resistive memory device applications and nanoscale thermo-optical management. Specific case studies that will be presented include the characterization of weakly photoluminescent and curved carbon dots for memory device applications, the three-dimensional characterization of plasmon-enhanced nanophotonic devices, as well as the development of near-field thermoreflectance imaging for nanophotonic-based thermal management applications. Collectively, our study well represents the versability of SNOM as a unique super-resolution nanophotonic tool for the investigation of light-matter interaction at the nanoscale.

Enhanced magnetic anisotropy and its thermal stability in obliquely deposited Co-Film on the nanopatterned substrate

The deliberate manipulation of magnetic anisotropy through controlled adjustments to surface and interface morphology has become important due to its potential applications in spintronics and magnetic memory devices. In the present work, oblique angle deposition (OAD) at 65° to the surface normal on a rippled substrate, keeping nanopatterns on the SiO2 substrate perpendicular to the OAD projection, has been used to induce in-plane uniaxial magnetic anisotropy (UMA) and its thermal stability in cobalt (Co) thin film. Prior to film preparation, the patterned substrate of wavelength 68 ± 4 nm and amplitude 3.4 ± 0.2 nm was prepared separately using a low-energy ion beam erosion (IBE) process. Grazing incidence small-angle X-ray scattering (GISAXS) and magneto-optical Kerr effect (MOKE) techniques have been used for film characterization. While GISAXS provided information about film structure and morphology, MOKE provided information about magnetic properties, thus making it possible to correlate the temperature-dependent evolution of morphology with that of UMA in the film. A clear anisotropy in the growth of Co film is found to result in strong UMA. Unlike previous studies, which typically observe a reduction in UMA strength with thermal annealing, the present work demonstrates a 31 % increase in UMA strength after annealing up to 200 °C, underscoring the importance of oblique angle deposition on nano-rippled substrates for achieving high UMA and ensuring its thermal stability up to moderate temperatures. The appearance of large UMA and its unusual temperature dependence is understood in terms of the shadowing effects and column coalescence, resulting in more robust shape anisotropy. This work provides insights into morphological anisotropy, elucidating the interplay of shadowing effects, shape anisotropy, and dipolar interactions within interacting column and ripple structures. This method gives rise to morphology-induced anisotropy, which can also be applied to other ferromagnetic films to enhance the magnetic anisotropy and ensure thermal stability.

Evidence of self-biased magnetoelectric coupling in eco-friendly (Na0.41K0.09Bi0.5TiO3-Ba0.85Ca0.15Zr0.1Ti0.9O3)-(CoFe2O4) particulate composites

The magnetoelectric (ME) properties of eco-friendly 1-x(0.94Na0.41K0.09Bi0.5TiO3-0.06Ba0.85Ca0.15Zr0.1Ti0.9O3)-x (CoFe2O4) (NKBCZT-CFO) with x = 0, 0.1, 0.2, 0.3 and 0.4 particulate composites were investigated. The X-ray diffraction studies provided evidence for the simultaneous existence of constituent phases (ferroelectric and ferromagnetic) in the composite. The structural and surface morphology analysis of the composite affirmed the homogeneous and densely packed distribution of CFO grains within the NKBCZT matrix. The composite's multiferroic behavior at room temperature was confirmed through the characterization of P vs E and M vs H hysteresis loops. The observed values of remnant polarization (Pr) and coercive field (Ec) are 26.7 μC/cm2 and 35.5 kV/cm, respectively, for 10 mol% of CFO. The increase in CFO content resulted in a decrease in the ferroelectric properties, possibly due to the conductive behaviour exhibited by CFO, and correlated with leakage current measurement. For the composite containing 40 mol% of CFO, the estimated values of remanent (Mr), saturation (Ms) magnetization, coercive field (Hc), and magnetic moment (µB) are 2.35 emu/g, 21.85 emu/g, 104.2 Oe, and 0.86 µB, respectively. The non-Debye type dielectric relaxation processes have been observed in the composites, and the electron hopping mechanism resulted in a higher dielectric constant (εʹ). Enhancement in relaxor nature had been observed through Vogel-Fulcher analysis with CFO content. The evidence of ME coupling was revealed through the direct ME voltage coefficient (αME) and magnetocapacitance (MC) measurement. The observed maximum value of MC measured at 1 kHz for the 20 mol% CFO is ∼5.6 %. Self-biased ME coupling (non-zero αME at HDC = 0 Oe) was observed in 20 and 30 mol% of CFO composite. The highest measured value of αME for 20 and 30 mol% CFO is 3.63 mV/cm.Oe and 4.09 mV/cm.Oe at HDC = 0 Oe respectively. The strong ME interaction and significant value of self-biased ME αME suggest that these composites can be explored for magnetic sensor and ME memory device applications.

Dielectric Properties and Carrier Transport Mechanism in Annealed HfOx‐Based Resistive Random Access Memory Devices

The diversity of the carrier transport mechanism in the resistive switching process remains a significant obstacle for the design and application of resistive random access memory (RRAM) devices. In this study, the influence of annealing on the dielectric properties of the Ti/HfOx/Pt RRAM device and its associated carrier transport mechanism is investigated. The results reveal that the current conduction in both annealed and unannealed devices is primarily attributed to grain boundary (GB) relaxation, with only the GB acting as a depletion layer that induces dielectric relaxation. Furthermore, annealing decreases the interfacial polarization and changes the relaxation time at the GB. In addition, the charge carriers exhibit nearest‐neighbor hopping conduction at a higher temperature in Ti/HfOx/Pt RRAM devices, whereas variable‐range‐hopping conduction occurs at lower temperatures. Long‐range charge carrier transport also plays a significant role in the conduction process. To offer a deeper understanding of the conduction processes in the Ti/HfOx/Pt RRAM device, a carrier transport model is proposed, which provides valuable insights into the intricate mechanisms governing conduction in these devices.

Magnetic Switching Dynamics and Tunnel Magnetoresistance Effect Based on Spin-Splitting Noncollinear Antiferromagnet Mn3Pt

In comparison to ferromagnets, antiferromagnets are believed to have superior advantages for applications in next-generation magnetic storage devices, including fast spin dynamics, vanishing stray fields and robust against external magnetic field, etc. However, unlike ferromagnetic orders, which could be detected through tunneling magnetoresistance effect in magnetic tunnel junctions, the antiferromagnetic order (i.e., Néel vector) cannot be effectively detected by the similar mechanism due to the spin degeneracy of conventional antiferromagnets. Recently discovered spin-splitting noncollinear antiferromagnets, such as Mn3Pt with momentum-dependent spin polarization due to their special magnetic space group, make it possible to achieve remarkable tunneling magnetoresistance effects in noncollinear antiferromagnetic tunnel junctions. Through first-principles calculations, we demonstrate that the tunneling magnetoresistance ratio can reach more than 800% in Mn3Pt/perovskite oxides/Mn3Pt antiferromagnetic tunnel junctions. We also reveal the switching dynamics of Mn3Pt thin film under magnetic fields using atomistic spin dynamic simulation. Our study provides a reliable method for detecting Néel vector of noncollinear antiferromagnets through the tunnel magnetoresistance effect and may pave its way for potential applications in antiferromagnetic memory devices.

Opportunity of ferrimagnetic (CZLF)/ferroelectric (BZT) composite materials in high frequency applications

AbstractThe ferrimagnetic Zn0.35Co0.65 La0.02Fe1.98O4 (CZLF) ferrite with cubic spinel structure (space group Fd3m) was made into composite by mixing with ferroelectric Ba0.5Zr0.5TiO3 (BZT) perovskite with tetragonal structure (space group P4mm) at the mass ratio. Disk-shaped composite powder was finally heated at 1100 °C to study the structure, dielectric and ferroelectric properties. The structural characterization for synthesized samples were carried out using Fourier transform infrared and Transmission Electron Microscopy. Fourier transform infrared show the successful formation of composite samples which is also observed from x-ray diffraction pattern. In compared to their ferrite counterparts before the composite, dielectric response and ferroelectric characteristics of the composite samples are noticeably altered. Compared to the ferrite samples, the composite system exhibits a higher permittivity. In composite samples, the space charge polarization, which was primarily effective at low frequencies and high measurement temperatures, is much diminished. The mechanical properties and indentation creep of these bearing alloys were studied by Vickers indentation testing at room temperature. The remnant polarization of BZT/CZLF increases with decreasing BZT content, which may be suitable for permanent memory device applications. Graphical abstract

Optical Modulation of MoTe2/Ferroelectric Heterostructure via Interface Doping.

Optical modulation through interface doping offers a convenient and efficient way to control ferroelectric polarization, thereby advancing the utilization of ferroelectric heterostructures in nanoelectronic and optoelectronic devices. In this work, we fabricated heterostructures of MoTe2/BaTiO3/La0.7Sr0.3MnO3 (MoTe2/BTO/LSMO) and demonstrated opposite ultraviolet (UV) light-induced polarization switching behaviors depending on the varied thicknesses of MoTe2. The thickness-dependent band structure of MoTe2 film results in interface doping with opposite polarity in the respective heterostructures. The polarization field of BTO interacts with the interface charges, and an enhanced effective built-in field (Ebi) can trigger the transfer of massive UV light-induced carriers in both MoTe2 and BTO films. As a result, the interplay among the contact field of MoTe2/BTO, the polarization field, and the optically excited carriers determines the UV light-induced polarization switching behavior of the heterostructures. In addition, the electric transport characteristics of MoTe2/BTO/LSMO heterostructures reveal the interface barrier height and Ebi under opposite polarization states, as well as the presence of inherent in-gap trap states in MoTe2 and BTO films. These findings represent a further step toward achieving multifield modulation of the ferroelectric polarization and promote the potential applications in optoelectronic, logic, memory, and synaptic ferroelectric devices.

Inherent D-A Architecture in Indoloquinoxalines with an Array of Substituents for Non-Volatile Memory Device Applications.

Donor-acceptor (D-A)-based architecture has been the key to increase storage capability efficiency through the enhanced charge transportation in the fabricated device. We have designed and synthesized a series of functionalized indoloquinoxalines (IQ) for non-volatile organic memory devices. The investigation on UV-visible spectra reveals the absorption maxima of the compounds around 420 nm, attributed to the intramolecular charge transfer between indole and quinoxaline moiety. The irreversible anodic peak in the 1.0 to 1.5 V range indicates the indole moiety's oxidation ability. Besides, the cathodic peak in the range of -0.5 to -1.0 V, contributed to the stability of the reduced quinoxaline unit. All the compounds exhibited uniformly covered thin film in SEM analysis, potentially facilitating the seamless charge carrier migration between adjacent molecules. The methoxyphenyl substituted compound exhibited the binary write-once read-many (WORM) memory behavior with the lowest threshold voltage of -0.81 V. The molecular simulations displayed the efficient intramolecular charge transfer, providing the fabricated device's distinctive conductive states. Except for the tert-butylphenyl compound, which showed volatile dynamic random-access memory (DRAM) behavior, all the other compounds exhibited non-volatile WORM memory behavior, suggesting IQs potential as an intrinsic D-A molecule in organic memory devices on further structural refinement.

Investigation of structural and electronic properties of double perovskites A2LnRuO6 (A = Ba, Ca; Ln = Eu, Dy)

Using density functional theory, we investigated the structural, vibrational, and electronic properties of A2LnRuO6 (A = Ba, Ca; Ln = Eu, Dy) double perovskite oxides using GGA and GGA+U exchange-correlation approximations. Ba2LnRuO6 double perovskites exhibit a structure with cubic ( Fm3¯m ) symmetry, whereas Ca2LnRuO6 compounds have monoclinic (P21/n) symmetry. Raman spectroscopy analysis shows stability and the presence of A1g , E g and 2F2g modes for Ba2LnRuO6, while for Ca2LnRuO6, the observed Raman active modes are A g and B g . A2LnRuO6 shows semiconducting nature with an electronic band gap in the range of 1.3 eV-3.27 eV with GGA+U calculations. The spin-polarized calculations indicate the presence of strong magnetic behaviour with magnetic moment equal to 3 μ B /unit cell for Ba2LnRuO6 and 6 μ B /unit cell for Ca2LnRuO6. The spin-up and spin-down states show different band gap values so these compounds can be useful for applications in spintronics and magnetic memory devices.

Electronic and transport properties of boron and nitrogen passivated zigzag graphene nanoribbons

A systematic study is conducted on 8ZGNR by edge terminations with boron and nitrogen at I and II termination sites by replacing hydrogen atoms in a single layer and in two probe systems. Electronic properties were observed in the DFT framework. Non-equilibrium green’s function (NEGF) tool was used to study the transport properties. Analysis of band structure, total energy, formation energy, and projected density of states (PDOS) suggest that despite Boron and Nitrogen passivation at all the termination sites, the electronic behavior of the system remains metallic. The analysis of Transmission spectra also confirms its metallic behavior in all these cases. This study reveals that B and N passivated graphene nanoribbons are sensitive to electronic transmission. This fact makes it potentially useful for application in sensors, memory devices and many other nano-electronic devices.

Effect of nickel doping on magnetic and dielectric properties of orthorhombic calcium ferrite nanoparticles

Nickel (10∼50 mol%) doped calcium ferrite nanoparticles (NPs) are synthesized by the solution combustion method using lemon juice extract as a reducing agent, followed by calcination at 500°C. The calcined samples are characterized with different techniques. The Bragg reflections of Nickel doping confirm the formation of a single orthorhombic calcium ferrite phase. The crystallite size is estimated using both Scherrer's and the W-H plot method. The surface morphology consists of irregular size and shaped agglomerated NPs along with pores and voids. A blueshift and a broad absorption spectrum is observed with an increase in the direct energy band gap. The direct energy band gap estimated from Wood and Tauc's relationship was found to be 2.91∼2.97 eV with an increase in dopant concentration. The magnetic analysis provided values for saturation magnetization (Ms), remanence (Mr), and coercivity (Hc), while dielectric studies demonstrated a dielectric constant of 2.81, 2.14, and 1.67 with increasing dopant concentration. The variation of dielectric properties of the sample as a function of frequency in the range 0.1∼20 MHz has been studied at room temperature. The dielectric properties of CaFe2O4: Ni (1∼9 mol%) NPs clearly indicate that there is a more pronounced dispersion at lower frequencies, gradually reaching saturation as the frequency increases. The dielectric loss was found to decrease from 4.62, 3.22, and 2.32 with an increase in Ni2+ substitution (10, 30, and 50 mol%) respectively. These results indicate the suitability of these samples for applications in memory devices and high-frequency applications.

A High Working Temperature Multiferroic Induced by Inverse Temperature Symmetry Breaking.

Molecular-based multiferroic materials that possess ferroelectric and ferroelastic orders simultaneously have attracted tremendous attention for their potential applications in multiple-state memory devices, molecular switches, and information storage systems. However, it is still a great challenge to effectively construct novel molecular-based multiferroic materials with multifunctionalities. Generally, the structure of these materials possess high symmetry at high temperatures, while processing an obvious order-disorder or displacement-type ferroelastic or ferroelectric phase transition triggered by symmetry breaking during the cooling processes. Therefore, these materials can only function below the Curie temperature (Tc), the low of which is a severe impediment to their practical application. Despite great efforts to elevate Tc, designing single-phase crystalline materials that exhibit multiferroic orders above room temperature remains a challenge. Here, an inverse temperature symmetry-breaking phenomenon was achieved in [FPM][Fe3(μ3-O)(μ-O2CH)8] (FPM stands for 3-(3-formylamino-propyl)-3,4,5,6-tetrahydropyrimidin-1-ium, which acts as the counterions and the rotor component in the network), enabling a ferroelastoelectric phase at a temperature higher than Tc (365 K). Upon heating from room temperature, two-step distinct symmetry breaking with the mm2Fm species leads to the coexistence of ferroelasticity and ferroelectricity in the temperature interval of 365-426 K. In the first step, the FPM cations undergo a conformational flip-induced inverse temperature symmetry breaking; in the second step, a typical ordered-disordered motion-induced symmetry breaking phase transition can be observed, and the abnormal inverse temperature symmetry breaking is unprecedented. Except for the multistep ferroelectric and ferroelastic switching, this complex also exhibits fascinating nonlinear optical switching properties. These discoveries not only signify an important step in designing novel molecular-based multiferroic materials with high working temperatures, but also inspire their multifunctional applications such as multistep switches.

Frequency dependence of wake-up and fatigue characteristics in ferroelectric Al0.93B0.07N thin films

B-doped AlN ferroelectric thin films are promising candidates for non-volatile memory device applications, due to their relatively low deposition temperatures, large remanent polarizations (up to 120 μC/cm2), and outstanding polarization retention properties. In this research, the polarization switching fatigue characteristics in epitaxial B-doped AlN thin films were investigated. Films were deposited via reactive RF magnetron sputtering onto W-coated c-plane sapphire substrates. Polarization switching fatigue measurements were conducted with triangular waveforms for frequencies between 50 and 1000 Hz from room temperature to 200°C. On repeated cycling, the films undergo wake-up; the wake-up process was characterized by an activation energy of 0.15 ± 0.05 eV. After a period of normal switching, the film leakage current increased with additional cycling, and finally the films underwent dielectric breakdown. Unpatterned Al0.93B0.07N films with 100 nm thick Pt top electrodes survived ∼104 bipolar cycles, whereas films with 1000 nm W top electrodes survived ∼105 cycles before dielectric breakdown. Modeling was used to design a field plate, which improved the performance to ∼106 fatigue cycles. It was found that dielectric failure during fatigue was not due to surface flashover but was associated with hard breakdown events in the dielectric. Failure for 100 Hz cycling was not associated with device self-heating but was exacerbated by field concentrations; at higher frequencies, the instantaneous temperature rise during the switching becomes prominent. Based on the fatigue process under 100 Hz under various ambient temperatures, the activation energy of the polarization switching fatigue of B-doped AlN thin films was found to be Ea = 0.10 ± 0.03 eV.

High-performance nano-scale InSnO transistors

Nanoscale short-channel oxide thin film transistors (TFTs) have attracted widespread research interest due to their potential applications in advanced display and memory devices. In this work, we fabricate 10 μm channel length indium-tin-oxide (ITO) TFTs and analyze the uniformity and repeatability of ITO TFTs at the long channel range. Then we fabricate ITO TFTs with a series of channel lengths ranging from 10 μm to 150 nm and through an optimized process we finally fabricate 130 nm channel length high-performance ITO TFTs with an on-state current of 93 (μA/μm), a subthreshold swing of 102 (mV decade–1), and on/off ratio over 107 at a drain voltage of 3 V.

Photoinduced growth of the crystalline phase of tellurium on a 1T′-MoTe2 matrix

Due to the growing demand for miniaturization and energy efficiency in modern electronic devices, there is a renewed interest for optoelectronic memories and sensors based on 2D materials. In particular, the molybdenum ditelluride (MoTe2) is one of the most promising materials for applications in nonvolatile phase-change memory devices, as its properties can be controlled by visible-light illumination. Among the several ways to synthesize MoTe2, the molybdenum oxide tellurization through isothermal close space sublimation (CSS) annealing in gas atmosphere is a simple and low-cost effective method for large-scale production of devices based on this layered material. Therefore, the understanding of the physical properties of MoTe2 thin films produced by this technique is crucial for future applications. Surprisingly, our results indicate that there is a photoinduced growth of the crystalline phase of tellurium on the 1T′-MoTe2 matrix even when the power density of the laser is low. From Raman spectroscopy investigations, we were able to show that nanometer-sized tellurium crystallites work as seed sites for the photocrystallization of tellurium. By assuming that the overall crystallization process is described by a kinetic approach that is based on the Kolmogorov–Johnson–Mehl–Avrami theory, our results indicate that the process is governed by an anisotropic organization of the tellurium atoms in helical structures during the crystal growth.

High tunneling electroresistance in ferroelectric tunnel junctions based on two-dimensional α-In2Se3/MoTe2 van der Waals heterostructures.

Ferroelectric polarization-controlled band alignment can be realized in van der Waals heterostructures (vdWHs), which can be used to create new types of ferroelectric tunnel junctions (FTJs). In this work, we design six probable configurations of two-dimensional vdWHs based on a two-dimensional α-In2Se3 ferroelectric material which has two opposite polarization states P↑ and P↓, and the semiconductor MoTe2. First-principles calculations show robust ferroelectric polarization-controlled switching behavior between the high conductance state in configuration AA-P↓ and the low conductance state in configuration AA-P↑ in the most stable AA stacked vdWHs. Based on this vdWH, a two-dimensional transverse FTJ with AA-P↓ or AA-P↑ as the tunneling barrier and (In0.5Sn0.5)2Se3 monolayers (n-type doped) as electrodes is designed. The tunneling electroresistance ratio of the FTJs at the Fermi level reaches 1.22 × 104% when the tunneling barrier contains two repeating units N = 2 and can be greatly increased by increasing the thickness of the ferroelectric layer. Analysis of the work function, charge redistribution, and local density of states is performed to interpret the above phenomena. The findings suggest the great potential of the AA stacked α-In2Se3/MoTe2 vdWH in the design of high-performance FTJs and application in high-density non-volatile memory devices.

Spectral and temporal atomic coherence interaction in Eu3+ : NaYF4 and Eu3+ : BiPO4.

We investigate the spectral and temporal atomic coherence interaction based on out-of-phase fluorescence (FL) and spontaneous parametric four-wave mixing (SFWM) from the hexagonal phase of Eu3+ : NaYF4 and different phases of Eu3+ : BiPO4. Spectral and temporal interactions are interrelated and reduced by about 2 times due to two-photon nested dressing in contrast to the sum of each laser excitation. As the lifetime of photons increases, off-resonance profile cross-interaction decreases because cross-interaction reverses the signal at the near time gate position and keeps it consistent at the far time gate position. Moreover, the thermal phonon dressing at 300 K exhibits 6 times more eminent and obvious temporal interaction than that at 77 K. In a different phase of Eu3+ : BiPO4, there are three dark dips having stronger self-interaction; however, Eu3+ : NaYF4 has two dark dips as Eu3+ : BiPO4 has two phonon dressing. Further, the pure hexagonal phase of Eu3+ : BiPO4 demonstrates the strongest cross-interaction and longest coherent time under the dressing effect due to the smallest dressing phonon detuning and off-resonance profile cross-interaction at PMT2 because the angle quantization is the strongest. Such results can be used for designing novel quantum devices and have potential applications in quantum memory devices.

Investigation of the structure and dielectric properties of doped barium titanates.

This work examined the influence of zirconium concentration on barium titanate (BZT) BaZrxTi1-xO3, with (x = 0, 0.15, 0.50, 0.75, and 1), produced by the tartrate precursor technique. The Fourier transform infrared (FTIR) spectra support the X-ray diffraction (XRD) results regarding formation of the perovskite structure. Grain size grows with Zr concentration, suggesting that the presence of Zr ions enlarges the grains. The transmission electron microscopy (TEM) images demonstrated that, due to their nano size, nanocrystallites are agglomerated in most images with irregular morphologies and average particle sizes from 20.75 nm to 63.75 nm. Increasing Zr content diminished the piezoelectric coefficient (d33) and the grain size. The value of d33 decreases by increasing Zr content, and there is an inverse relationship between grain size and d33. The remnant polarization of BZT increases with increasing Zr4+ content, which may be suitable for permanent memory device applications.

(Invited) Fabrication Technique of Ferroelectric HfxZr1−XO2 Thin Films Using ALD-ZrO2 Nucleation Layers

Ferroelectric HfxZr1−xO2 (HZO) thin films have attracted considerable attention towards high-density and low-power ferroelectric memory devices of ferroelectric random access memory (FeRAM) and ferroelectric field-effect transistors (FeFETs) [1]. To obtain ferroelectric orthorhombic (O) phase of HZO films, several techniques have been investigated, such as the TiN stressor layer technique [2] and controlled annealing conditions [3]. On the other hand, we pay attention to the ZrO2 nucleation layer technique because ZrO2 films deposited by atomic layer deposition (ALD) method formed a nanocrystalline structure and consisted dominantly of O, tetragonal (T), and cubic (C) phases, whose lattice constants are considerably close to that of ferroelectric O phase for HfO2 [4]. In this paper, we report the crystallinity and ferroelectricity of HZO films fabricated using the ZrO2 nucleation layer technique for metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors.First, four types of MFM capacitors of TiN/HZO/TiN (MFM w/o), TiN/HZO/bottom-ZrO2/TiN (MFM B-ZrO2), TiN/top-ZrO2/HZO/TiN (MFM T-ZrO2), and TiN/top-ZrO2/HZO/bottom-ZrO2/TiN (MFM D-ZrO2) were systematically investigated for the FeRAM applications [5]. The thicknesses of the ALD-grown HZO and ZrO2 films were 10 and 2 nm, respectively. The post-deposition annealing was performed at 600°C. The remanent polarization (2P r = P r + − P r −) of the MFM capacitors increased in the following order: MFM w/o (12 µC/cm2) < MFM B-ZrO2 (15 µC/cm2) < MFM T-ZrO2 (23 µC/cm2) < MFM D-ZrO2 (29 µC/cm2), while all capacitors showed almost the same coercive electric field (E c) value of around 1.2 MV/cm. Therefore, maximum 2P rvalue of the MFM capacitor was obtained using the top- and bottom-ZrO2 nucleation layers. For the MFM capacitors with ZrO2 nucleation layers, epitaxial-like grain growth of the HZO film occurred on the nanocrystalline top- and bottom-ZrO2 layers. Moreover, the relative ratio of O/T/C phases in the ferroelectric film, which was estimated using the peak area ratio of O(111)/T(101)/C(111)/{M(−111)+ O(111)/T(101)/C(111)+M(111)}, increased in the following order: MFM w/o < MFM B-ZrO2 < MFM T-ZrO2 < MFM D-ZrO2. Therefore, the top- and bottom-ZrO2 layers play an important role as nucleation layers for the crystallization of the HZO film, resulting in a larger relative ratio of O/T/C phases in the ferroelectric film compared to w/o. Moreover, these results indicate that the top-ZrO2 layer was more effective to form the ferroelectric phase compared to the bottom-ZrO2 layer.Next, two types of MFS capacitors of TiN/HZO/Si (MFS w/o) and TiN/top-ZrO2/HZO/Si (MFS T-ZrO2) were fabricated by low-temperature processes at 300°C of ALD and post-metallization annealing (PMA) for the FeFET applications [6]. The thicknesses of both HZO and ZrO2 films were 10 nm. Both MFS w/o and MFS T-ZrO2 were found to form an extremely thin SiO2 interfacial layer with a thickness of one or two monolayers between the HZO film and Si substrate due to a low temperature fabrication process of 300°C. The HZO film of the MFS T-ZrO2 formed O/T/C phases even with a low thermal budget of 300°C, while that of the MFS w/o had an amorphous structure. This result is attributed to the beneficial role of the nanocrystalline top-ZrO2 nucleation layer for the crystallization of an amorphous HZO film during the PMA process. Therefore, a higher 2P r value of 15 µC/cm2 was obtained for the MFS T-ZrO2 than that (2.2 µC/cm2) for the MFS w/o. Moreover, the endurance properties of the MFS T-ZrO2 were free from the wake-up effect and exhibited less degradation of switching polarization (P sw). This could be attributed to the insertion of a ZrO2 film at the TiN/HZO interface, which promoted the preferential formation of the ferroelectric orthorhombic phase and prevent the formation of oxygen vacancies at the ZrO2/HZO interface. Thus, we concluded that superior ferroelectricity with wake-up free properties and higher fatigue resistance of HZO-based MFS capacitors were achieved by using the ZrO2 nucleation layer technique.These results suggest that the fabrication technique of ferroelectric HZO films using nanocrystalline ALD-ZrO2 nucleation layers is one of the promising processes for the next-generation non-volatile memory device applications.This work was supported by JSPS KAKENHI (Nos. JP21J01667, JP20H02189, and JP18J22998) and MEXT Leading Initiative for Excellent Young Researchers (No. JPMXS0320220213).[1] T. Mikolajick et al., J. Appl. Phys. 129, 100901 (2021).[2] S. J. Kim, et al., Appl. Phys. Lett. 111, 242901 (2017).[3] S. Migita et al., Jpn. J. Appl. Phys. 58, SBBA07 (2019).[4] T. Onaya et. al., Appl. Phys. Express. 10, 081501 (2017).[5] T. Onaya et al., APL Mater. 7, 061107 (2019).[6] T. Onaya et al., APL Mater. 10, 051110 (2022).