Next-generation Nonvolatile Memory Research Articles

Manganite memristive devices: recent progress and emerging opportunities

Manganite-based memristive devices have emerged as promising candidates for next-generation non-volatile memory and neuromorphic computing applications, owing to their unique resistive switching behavior and tunable electronic properties. This review explores recent innovations in manganite-based memristive devices, with a focus on materials engineering, device architectures, and fabrication techniques. We delve into the underlying mechanisms governing resistive switching in manganite thin films, elucidating the intricate interplay of oxygen vacancies, charge carriers, and structural modifications. This review underscores breakthroughs in harnessing manganite memristors for a range of applications, from high-density memory storage to neuromorphic computing platforms that mimic synaptic and neuronal functionalities. Additionally, we discuss the role of characterization techniques and the need for a unified benchmark for these devices. We provide insights into the challenges and opportunities associated with the co-integration of manganite-based memristive devices with more mature technologies, offering a roadmap for future research directions.

Subthreshold read operations in 3D PCM: 1S1R device modeling and memory array analysis

3-D phase change memory (PCM) is one of the most promising next-generation nonvolatile memory, and the subthreshold sensing strategy can effectively improve its limited endurance. In this study, we propose a one-selector-one-resistor (1S1R) model with Monte Carlo (MC) function and provide array configurations for the worst case and the maximum bit line voltage (VBL-max), respectively. Based on these, the read window margin (RWM) is evaluated with various array sizes, OTS threshold voltage variations (σvar), and bias voltages (VBias). Our results reveal that the RWM increases as the VBL approaches the VBL-max. Larger arrays lead to an increased leakage current difference, while larger σvar values result in decreased cell current difference and VBL-max. The decrease in VBL-max further deteriorates the RWM. Additionally, we analyze the optimal VBias for 2-deck arrays achieves a 7% reduction in leakage energy consumption and a 22.6% increase in RWM compared to the V/2 bias. The optimal VBias depends on OTS devices and array sizes.

Influence of local structures on amorphous alumina exhibiting resistance random-access memory function

Amorphous alumina resistance random-access memory is a promising candidate as a next-generation nonvolatile memory. It is intriguing that the nonvolatile memory function emerges in only amorphous samples, unlike crystalline samples. We studied local structures of amorphous alumina samples and Al2O3 polycrystalline using atomic pair distribution function measurements. We derived the Al–Al, O–O, and Al–O atomic distances for each sample. By comparing them, we revealed that the subtle difference in the local structure significantly influences the performance of a nonvolatile memory function.

Ultrafast high-endurance memory based on sliding ferroelectrics.

The persistence of voltage-switchable collective electronic phenomena down to the atomic scale has extensive implications for area- and energy-efficient electronics, especially in emerging nonvolatile memory technology. We investigate the performance of a ferroelectric field-effect transistor (FeFET) based on sliding ferroelectricity in bilayer boron nitride at room temperature. Sliding ferroelectricity represents a different form of atomically thin two-dimensional (2D) ferroelectrics, characterized by the switching of out-of-plane polarization through interlayer sliding motion. We examined the FeFET device employing monolayer graphene as the channel layer, which demonstrated ultrafast switching speeds on the nanosecond scale and high endurance exceeding 1011 switching cycles, comparable to state-of-the-art FeFET devices. These characteristics highlight the potential of 2D sliding ferroelectrics for inspiring next-generation nonvolatile memory technology.

Zeolitic-imidazolate framework (ZIF-67) based bipolar memristor for nonvolatile ReRAM application

In the realm of next-generation nonvolatile memories, there is a strong demand for resistive random access memory (ReRAM) devices that are affordable, stable, and simple to produce. Metal–organic frameworks (MOFs) have garnered extensive research attention across diverse fields due to their remarkable chemical adaptability, stability, and exceptional structural variability. In this work, a ReRAM device has been fabricated that incorporates a solution-processed thin film of zeolitic imidazolate framework (ZIF-67), a material of MOFs class, as the resistive switching (RS) layer. This Al/ZIF-67/ITO structured device possesses a consistent RS behavior with a high on/off resistance ratio of ∼104. The retention of low resistance state and high resistance state have been shown up to 104 s. Furthermore, the device also shows a consistent switching for 500 cycles of pulse switching signals of +6 V/−1.8 V (set/reset). Based on the impedance spectroscopy analysis, a filamentary switching mechanism has been established for the RS behavior of the device. The robust and enduring performance, coupled with the substantial on/off resistance ratio and high retention of the states, makes this device a promising candidate for nonvolatile ReRAM applications.

Nanocrystal Materials for Resistive Memory and Artificial Synapses: Progress and Prospects.

Resistive random-access memory (RRAM) is considered to be the most promising next-generation non-volatile memory because of its low cost, low energy consumption, and excellent data storage characteristics. However, the on/off (SET/RESET) voltages of RRAM are too random to replace the traditional memory. Nanocrystals (NCs) offer an appealing option for these applications since they combine excellent electronic/optical properties and structural stability and can address the requirements of low-cost, large-area, and solution-processed technologies. Therefore, the doping NCs in the function layer of RRAM are proposed to localize the electric field and guide conductance filaments (CFs) growth. The purpose of this article is to focus on a comprehensive and systematical survey of the NC materials, which are used to improve the performance of resistive memory (RM) and optoelectronic synaptic devices and review recent experimental advances in NC-based neuromorphic devices from artificial synapses to light-sensory synaptic platforms. Extensive information related to NCs for RRAM and artificial synapses and their associated patents were collected. This review aimed to highlight the unique electrical and optical features of metal and semiconductor NCs for designing future RRAM and artificial synapses. It was demonstrated that doping NCs in the function layer of RRAM could not only improve the homogeneity of SET/RESET voltage but also reduce the threshold voltage. At the same time, it could still increase the retention time and provide the probability of mimicking the bio-synapse. NC doping can significantly enhance the overall performance of RM devices, but there are still many problems to be solved. This review highlights the relevance of NCs for RM and artificial synapses and also provides a perspective on the opportunities, challenges, and potential future directions.

Conversion between digital and analog resistive switching behaviors and logic display application of photoresponsive ZnO nanorods-based memristor

Memristors have shown great application prospects in next-generation non-volatile memory (NVMs) and brain-inspired computing systems, but various application prospects have different requirements for device performance. Currently, it is difficult to precisely regulate the conversion of memristive effects between analog and digital due to the complex resistive switching mechanism. In this work, size-controlled ZnO nanorods was achieved by adjusting the concentration of the surfactant polyethyleneimine (PEI), and further research was conducted for the memristive effect of the as-prepared memristors based on ZnO nanorods with different sizes. The results showed that PEI accelerates the protonation process, leading to the increase of OH– ions, which further leads to the transition of the memristive effect of the as-prepared device from digital to analog as the PEI concentration increases. Moreover, the optical controlled logic display function was achieved in the memristor based on the light-sensitive properties of the ZnO nanorods. Therefore, this work lays the foundation that the memristor with analog and digital memristive effect can control and enrich the application prospects of memristor.

A BaTiO3-based flexible ferroelectric capacitor for non-volatile memories

BaTiO3 (BTO) ferroelectric films, which are renowned for their lead-free compositions, superior stability, and absence of a wake-up effect, are promising candidate materials in the field of non-volatile memories. However, the prerequisites for high-temperature conditions in the fabrication of ferroelectric thin films impose constraints on the substrate choice, which has limited the advancement in non-volatile memories based on single-crystal flexible BTO films with robust ferroelectric properties. Herein, a technique has been developed for the fabrication of flexible devices using a pulsed laser deposition system. BTO ferroelectric films have then been deposited onto a flexible mica substrate, with SrTiO3 (STO) serving as a buffer layer. The obtained flexible BTO devices exhibited excellent ferroelectricity, with a maximum polarization (2Pmax) of up to 42.58 μC/cm2 and a remnant polarization (2Pr) of up to 21.39 μC/cm2. Furthermore, even after 1,000 bending cycles, the bipolar switching endurance remained high at 1012 cycles. After 104 s, the flexible BTO device still maintained excellent polarization characteristics. These results make the flexible BTO ferroelectric thin film a potential candidate for the next generation of non-volatile memories.

Phase-change heterostructure with HfTe2 confinement sublayers for enhanced thermal efficiency and low-power operation through Joule heating localization

Although phase-change random-access memory (PCRAM) is a promising next-generation nonvolatile memory technology, challenges remain in terms of reducing energy consumption. This is primarily because the high thermal conductivities of phase-change materials (PCMs) promote Joule heating dissipation. Repeated phase transitions also induce long-range atomic diffusion, limiting the durability. To address these challenges, phase-change heterostructure (PCH) devices that incorporate confinement sublayers based on transition-metal dichalcogenide materials have been developed. In this study, we engineered a PCH device by integrating HfTe2, which has low thermal conductivity and excellent stability, into the PCM to realize PCRAM with enhanced thermal efficiency and structural stability. HEAT simulations were conducted to validate the superior heat confinement in the programming region of the HfTe2-based PCH device. Moreover, electrical measurements of the device demonstrated its outstanding performance, which was characterized by a low RESET current (∼1.6 mA), stable two-order ON/OFF ratio, and exceptional cycling endurance (∼2 × 107). The structural integrity of the HfTe2 confinement sublayer was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The material properties, including electrical conductivity, cohesive energy, and electronegativity, substantiated these findings. Collectively, these results revealed that the HfTe2-based PCH device can achieve significant improvements in performance and reliability compared with conventional PCRAM devices.

Multi-bit MRAM based high performance neuromorphic accelerator for image classification

Binary neural networks (BNNs) are the most efficient solution to bridge the design gap of the hardware implementation of neural networks in a resource-constrained environment. Spintronics is a prominent technology among emerging fields for next-generation on-chip non-volatile memory. Spin transfer torque (STT) and spin-orbit torque (SOT) based magnetic random-access memory (MRAM) offer non-volatility and negligible static power. Over the last few years, STT and SOT-based multilevel spintronic memories have emerged as a promising solution to attain high storage density. This paper presents the operation principle and performance evaluation of spintronics-based single-bit STT and SOT MRAM, dual-level cells, three-level cells (TLCs), and four-level cells. Further, multi-layer perceptron architectures have been utilized to perform MNIST image classification with these multilevel devices. The performance of the complete system level consisting of crossbar arrays with various MRAM bit cells in terms of area, energy, and latency is evaluated. The throughput efficiency of the BNN accelerator using TLCs is 26.6X, and 3.61X higher than conventional single-bit STT-MRAM, and SOT-MRAM respectively.

Influence of interface on the domain polarization orientation in ferroelectric Hf0.5Zr0·5O2 thin films

Ferroelectric HfO2-based materials have attracted extensive attention in the research of next-generation nonvolatile memories and logic devices due to their superior scaling properties and compatibility with the CMOS process. However, forming the ferroelectric metastable phase in the thin films of a few nanometers requires clamping of the top and bottom electrodes. As a result, the interface can significantly impact domain structure and polarization, leading to imprinting effects and non-uniform space charge distribution. Here, we have demonstrated how the interface affects the ferroelectric polarization in Hf0.5Zr0·5O2 (HZO) thin films produced by ALD and the physical mechanisms behind it. We found that by regulating the quantity of oxygen vacancy content at the top and bottom interfaces of TiN/HZO/TiN ferroelectric capacitors, it is possible to achieve inversion of polarization orientation. By using a spherical aberration-corrected transmission electron microscope and first-principles calculation, we identified that the internal electric field generated by the accumulation of oxygen vacancies at an interface and the asymmetrical electrostatic energy of the interfacial T-phase layer jointly play a role in the ferroelectric polarization orientation. Our results will significantly help the interface engineering of HfO2-based ferroelectric thin films and devices.

Fabrication of high quality lead-free double perovskite Cs2AgBiBr6 thin film and its application in memristor with ultralow operation voltage

Recently, the lead-free double perovskite Cs2AgBiBr6 has been considered as a promising candidate for next-generation nonvolatile memory and artificial synapse devices due to its high stability and low toxicity compared to its lead-based counterparts. In this work, we developed a simple and effective method to produce high-quality lead-free double perovskite Cs2AgBiBr6 thin films without pinholes and particles by applying a low-pressure assisted method under ambient condition with a relative humidity (RH) of about 45%. The formation of pinholes and Ag precipitation in the perovskite Cs2AgBiBr6 films is effectively suppressed by the proper ratio of N,N-dimenthylformamide (DMF) mixed in dimethyl sulfoxide (DMSO) solvents. Furthermore, the grain size of the Cs2AgBiBr6 films can be significantly increased by increasing the post-annealing temperature. Finally, a sandwiched structure memristor with an ITO/Cs2AgBiBr6/Ta configuration was successfully demonstrated, featuring ultralow operation voltage (V Set ∼ 57 ± 23 mV, V Reset ∼ −692 ± 68 mV) and satisfactory memory window (the ratio of R HRS/R LRS ∼ 10 times), which makes it suitable for low-power consumption information storage devices.

Ferroelectricity in twisted double bilayer graphene

Two-dimensional (2D) ferroelectrics can maintain electrical polarization up to room temperature and are, therefore, promising for next-generation nonvolatile memories. Although natural 2D ferroelectrics are few, moiré superlattices provide us with a generalized method to construct ferroelectrics from non-ferroelectric parent materials. We report a realization of ferroelectric hysteresis in an AB-BA stacked twisted double bilayer graphene (TDBG) system. The ferroelectric polarization is prominent at zero external displacement field and reduces upon increasing displacement fields. TDBG in the AB-BA configuration is an intriguing system, which facilitates ferroelectricity even without the assistance of any boron nitride layers; however, in the AB-AB stacking case, the development of polarization necessitates the presence of a second superlattice induced by the adjacent boron nitride layer. Therefore, twisted multilayer graphene offers us a fascinating field to explore 2D ferroelectricity.

Thermally-induced nanoscale phase change in chalcogenide glass Cr2Ge2Te6 revealed by scanning tunneling microscopy

Cr2Ge2Te6 (CrGT) is viewed as an important phase change material (PCM) for next-generation nonvolatile memory devices because of its superior properties, e.g., high thermal stability and low operation energy, compared to conventional PCMs. However, the phase change mechanism of CrGT remains unsolved, especially at the nanoscale. Here, we investigated thermally induced nanoscale phase changes of CrGT thin films using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). By performing statistical analysis of the measured STM topographic and STS data, we evaluated the inhomogeneity and distribution of the phase change characteristics of CrGT thin films. We also related the nanoscale phase change properties of CrGT to macroscopic phase changes by comparing the STM and STS results with experimental data from Raman spectroscopy.

Kinetic Monte Carlo simulations on electroforming in nanomanipulated conductive bridge random access memory devices.

Conductive bridge random access memory (CBRAM) devices exhibit great potential as the next-generation nonvolatile memory devices. However, they suffer from two major disadvantages, namely relatively high power consumption and large cycle-to-cycle and device-to-device variations, which hinder their more extensive commercialization. To learn how to enhance their device performance, kinetic Monte Carlo (KMC) simulations were employed to illustrate the variation of electroforming processes in nanomanipulated CBRAM devices by introducing an ion-blocking layer with scalable nanopores and tuning the microstructures of dielectric layers. Both the size of nanopores and the inhomogeneity of dielectric layers have significant impacts on the forming processes of conductive filaments. The dielectric layer with a high-content loose texture plus the scalable nanopore-containing ion-blocking layer leads to the formation of size-controlled and uniform filaments, which remarkably contributes to miniaturizable and stable CBRAM devices. Our study provides insights into nanomanipulation strategies to realize high-performance CBRAM devices, still awaiting future experimental confirmation.

Selector-less crossbar array resistive RAM based on TiO2 fabricated by photochemical metal-organic deposition

In this study, we demonstrated a TiO2-based 32 × 32 crossbar array resistive RAM (ReRAM), a promising candidate for next-generation non-volatile memory (NVM), by utilizing a photochemical metal-organic deposition (PMOD) process. We achieved an interface-type resistive switching device with rectifying characteristics by controlling the oxidation state of directly patterned TiOx films through post-heat treatment. The photochemical reaction induced by UV in the PMOD process and the anatase phase formation during the post-heat treatment were analyzed using Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). XPS analysis revealed the immediate formation of Ti peroxide post-PMOD process, underscoring the efficacy of post-heat treatments in controlling oxidation states. Employing 350 °C annealed TiOX as the active material, we successfully fabricated a high-yield (93%), selectorless 32 × 32 crossbar array architecture for ReRAM. Our findings highlight the PMOD process as a viable, cost-effective alternative for memory devices, offering optimized oxidation states crucial for the performance of redox-based ReRAM.

(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).

Effect of Domain Structure and Dielectric Interlayer on Switching Speed of Ferroelectric Hf0.5Zr0.5O2 Film

The nanosecond speed of information writing and reading is recognized as one of the main advantages of next-generation non-volatile ferroelectric memory based on hafnium oxide thin films. However, the kinetics of polarization switching in this material have a complex nature, and despite the high speed of internal switching, the real speed can deteriorate significantly due to various external reasons. In this work, we reveal that the domain structure and the dielectric layer formed at the electrode interface contribute significantly to the polarization switching speed of 10 nm thick Hf0.5Zr0.5O2 (HZO) film. The mechanism of speed degradation is related to the generation of charged defects in the film which accompany the formation of the interfacial dielectric layer during oxidization of the electrode. Such defects are pinning centers that prevent domain propagation upon polarization switching. To clarify this issue, we fabricate two types of similar W/HZO/TiN capacitor structures, differing only in the thickness of the electrode interlayer, and compare their ferroelectric (including local ferroelectric), dielectric, structural (including microstructural), chemical, and morphological properties, which are comprehensively investigated using several advanced techniques, in particular, hard X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and electron beam induced current technique.

High-performance van der Waals antiferroelectric CuCrP2S6-based memristors

Layered thio- and seleno-phosphate ferroelectrics, such as CuInP2S6, are promising building blocks for next-generation nonvolatile memory devices. However, because of the low Curie point, the CuInP2S6-based memory devices suffer from poor thermal stability (<42 °C). Here, exploiting the electric field-driven phase transition in the rarely studied antiferroelectric CuCrP2S6 crystals, we develop a nonvolatile memristor showing a sizable resistive-switching ratio of ~ 1000, high switching endurance up to 20,000 cycles, low cycle-to-cycle variation, and robust thermal stability up to 120 °C. The resistive switching is attributed to the ferroelectric polarization-modulated thermal emission accompanied by the Fowler–Nordheim tunneling across the interfaces. First-principles calculations reveal that the good device performances are associated with the exceptionally strong ferroelectric polarization in CuCrP2S6 crystal. Furthermore, the typical biological synaptic learning rules, such as long-term potentiation/depression and spike amplitude/spike time-dependent plasticity, are also demonstrated. The results highlight the great application potential of van der Waals antiferroelectrics in high-performance synaptic devices for neuromorphic computing.

Infrared Signatures for Phase Identification in Hafnium Oxide Thin Films.

Phase identification in HfO2-based thin films is a prerequisite to understanding the mechanisms stabilizing the ferroelectric phase in these materials, which hold great promise in next-generation nonvolatile memory and computing technology. While grazing-incidence X-ray diffraction is commonly employed for this purpose, it has difficulty unambiguously differentiating between the ferroelectric phase and other metastable phases that may exist due to similarities in the d-spacings, their low intensities, and the overlapping of reflections. Infrared signatures provide an alternative route. However, their use in phase identification remains limited because phase control has overwhelmingly been accomplished via substituents, thereby convoluting infrared signatures between the substituents and the phase changes that they induce. Herein, we report the infrared optical responses of three undoped hafnium oxide films where annealing conditions have been used to create films consisting primarily of the ferroelectric polar orthorhombic Pca21, antipolar orthorhombic Pbca, and monoclinic P21/c phases, as was confirmed via transmission electron microscopy (TEM), UV-visible optical properties, and electrical property measurements. Vibrational signatures acquired from synchrotron nano-Fourier transform infrared spectroscopy (nano-FTIR) are shown to be capable of differentiating between the phases in a nondestructive, rapid, and nanoscale manner. The utility of nano-FTIR is illustrated for a film exhibiting an antiferroelectric polarization response. In this sample, it is proven that this behavior results from the Pbca phase rather than the often-cited tetragonal phase. By demonstrating that IR spectroscopy can unambiguously distinguish phases in this material, this work establishes a tool needed to isolate the factors dictating the ferroelectric phase stability in HfO2-based materials.