Self-powered photo-pyroelectric sensing in antiferroelectric Hafnium zirconium memory with asymmetric van der Waals electrodes

Domain: physics
Published: 2025-12-19
Editorial outcome: minor_revision

Abstract
Hafnium zirconium oxide with antiferroelectric polarizations holds great promise for emerging applications such as neuromorphic computing, energy-efficient storage, and nonvolatile memory, owing to its tunable phase transitions, fast switching speed, improved endurance, and excellent compatibility with silicon-based processes. In practical memory applications, however, the moderate residual polarizations of antiferroelectric hafnium zirconium oxide films pose greater challenges for nondestructive readout than their ferroelectric counterparts, particularly when relying solely on electrical pulses applied via metal electrodes. Here, we introduce graphite nanosheets as photoactive top electrodes for Hf0.1Zr0.9O2-based nonvolatile memories, enabling nondestructive optical readout through the photo-pyroelectric effect. The optothermally active van der Waals graphite nanosheet top electrode triggers nonpolar-to-polar state transition, thereby inducing a pyroelectric response in the Hf0.1Zr0.9O2 layer. This mechanism enables self-powered and nondestructive photo-pyroelectric sensing capabilities, as well as voltage-programmable in-memory logic functionalities—circumventing the destructive readout issues faced by traditional hafnium-based ferroelectrics. Our work paves the way for hafnium-zirconium-oxide-based, photonic-compatible memory architectures for post-Moore electronics.

Introduction
HfO2-based ferroelectric (FE) thin films demonstrate promising nonvolatile memory potential due to robust polarization retention at sub-10 nm thicknesses, inherent compatibility with state-of-the-art complementary metal-oxide-semiconductor (CMOS) technology, and high-density integration capability1–4. However, HfO2-based FE exhibits wake-up effects and fatigue issues, which may originate from depolarization fields or interface-related problems, consequently imposing challenges on widespread device applications5,6. To address these issues, Pešić et al. proposed a concept of antiferroelectric (AFE) nonvolatile memory (NVM), demonstrating that the built-in bias field can shift the hysteresis loop, allowing AFE materials to switch between polarized and non-polar states—thus laying a crucial theoretical and technical foundation for high-endurance memory development7,8. Recent experimental studies have indicated unique advantages of HZO-based AFE materials in NVM devices over FEs, including enhanced endurance and faster operational speeds9–11. However, to realize such performance, special device processes are required to engineer asymmetric work-functions (WFs) for top and bottom electrodes and thereby shift the polarization-voltage (P–V) curve to achieve FE-like characteristics and nonvolatile behavior, despite the inherent volatility of AFE films7,12,13. This WF-engineering technique involves a series of complex fabrication steps—such as deposition, annealing, wet etching, and re-deposition—which not only increase process complexity but also raise serious concerns, such as wet-etching-induced surface defects14 and degradation in device reliability, since the device performance is highly sensitive to the interfacial condition and properties. Thus, developing asymmetric electrodes (by using different materials to achieve distinct WFs) for AFE memories while maintaining high interfacial quality and device reliability remains highly challenging. Furthermore, the nondestructive readout of such nonvolatile AFE memories remains unresolved so far. The use of electrical pulses in conventional two-terminal devices for readout operations is inherently destructive, necessitating post-read rewriting, which significantly reduces the lifespan of HZO15.

Optical readout is a well-known nondestructive strategy. Nevertheless, reading the polarization states of HZO optically is challenging due to the inherent optical transparency of HfO2 (bandgap ≈ 5.8 eV)16. An effective approach is to couple the pyroelectric properties of HZO films with the photothermal response of the sandwiching electrodes. HZO exhibits pyroelectric behavior arising from its spontaneous polarization, where subtle thermal fluctuations induce changes in polarization strength, generating transient surface charges17–19. When this pyroelectric effect is combined with the photothermal response of the electrodes, a light-heat-electricity conversion mechanism can be established20–22: the photo-absorption of the electrodes causes a temperature rise in the device, which subsequently induces a measurable electrical response via the pyroelectric effect in the HZO films. Since the pyroelectric responsivity of HZO films depends on their polarization state8,23, this photo-pyroelectric mechanism enables optical readout for non-volatile memory devices. Notably, because it does not require any externally applied electrical pulses, this photo-pyroelectric readout is self-powered and thus inherently nondestructive. To date, photo-pyroelectric readout for detecting polarization states in hafnium-based ferroelectric devices has been explored, typically using bulky substrate electrodes (e.g., Si or Nb:SrTiO3) as the optical absorption layer24,25. However, beyond the required transparency of the top electrode and HZO layer, the temperature rise in such configurations is significantly suppressed due to efficient heat dissipation through the substrate’s high thermal conductivity, thereby degrading the photo-pyroelectric sensitivity. Moreover, it has been found that the remnant polarization (Pr) of FE HZO films is reduced compared to conventional metal–ferroelectric–metal (MFM) structures26,27. Thus, the applicability of the photo-pyroelectric readout scheme to HZO-based memory remains uncertain—particularly for AFE HZO memory, where its feasibility has not yet been examined.

In this work, we demonstrate that van der Waals integrated graphite nanosheets (GNS) can serve both as top asymmetric electrodes for AFE Hf0.1Zr0.9O2 NVM devices and as efficient photothermal harvesting layers28,29 to trigger the photo-pyroelectric effect, thereby enabling optically sensing functionality. The use of GNS as the top electrode facilitates efficient thermal energy transfer to the Hf0.1Zr0.9O2 layer under photo illumination. Transient photothermal excitation induces rapid temperature changes in the Hf0.1Zr0.9O2 before heat dissipates into the substrate, generating polarization-dependent short-circuit photocurrents measurable by external circuits. This optoelectronic response exhibits binary correlation with the programmed polarization states, establishing an optical readout mechanism that preserves structural integrity during non-destructive memory interrogation. Our devices exhibit wake-up-free operation, enhanced fatigue resistance, and voltage-programmable photo-pyroelectric response. The asymmetric GNS/W electrodes, combined with post-deposition annealing (PDA), establish a built-in bias field that shifts the polarization hysteresis loop of AFE Hf0.1Zr0.9O2 to enable two discrete polarization states. Compared with conventional work-function engineering approaches that require complex interface modifications, our method significantly reduces fabrication complexity while increasing photothermal conversion efficiency and, consequently, the reliability of photo-pyroelectric sensing. The two-terminal architecture offers superior integration potential over three-terminal field-effect transistor (FeFET) counterparts. This advance combines robust polarization switching with optical readability, addressing a critical trade-off between non-destructive readout capability and device scalability in HZO-based systems. Our demonstration provides a strategy for multifunctional memory devices that combine electrical programmability, photonics-compatible interfaces, and logic operations.

Results
Figure 1a shows the GNS/Hf0.1Zr0.9O2/W capacitor architecture: A 7.5 nm-thick Hf0.1Zr0.9O2 film sandwiched between a 25 nm GNS (top electrode/optical absorber) and 40 nm tungsten (W, bottom electrode). The simple architecture and mature ALD-based processes offer manufacturing scalability (fabrication details in Experimental Section and Supplementary Fig. 1). Figure 1b displays cross-sectional high-resolution transmission electron microscopy (HRTEM) imaging of the full stack, confirming the 7.5 nm built-in bias field engineering AFE layer with sharp GNS/Hf0.1Zr0.9O2 and Hf0.1Zr0.9O2/W interfaces. Atomic-resolution high-angle annular dark field (HAADF) scanning transmission electron microscope (STEM) image and simultaneously acquired integrated differential phase contrast (iDPC) image are presented in Fig. 1c, d, revealing the O-phase structure of the imaged nanocrystalline. The iDPC-STEM image, in particular, shows that half of the oxygen columns deviate from the central position of the four nearest Hf/Zr atoms, a typical character of the O-phase when viewed along the [010] zone axis1,6,30,31. The projected structure models are overlaid on the experimental images for comparison. Elemental analysis via energy-dispersive X-ray spectroscopy (EDX) mapping reveals the device composition. The elemental distribution of W, Hf, Zr, O, C, Cr, and Au elements is provided in Supplementary Fig. 2, showing co-localization between zirconium and oxygen. The spectrum from our devices (Supplementary Fig. 3) shows only the highly prominent G and 2D peaks characteristic of pristine graphite. This absence of spurious peaks indicates that our dry transfer process, which utilizes a PDMS stamp without any intermediate polymers, avoids chemical contamination32. The built-in bias field-engineered HZO heterostructure, realized through post-deposition annealing (PDA) and asymmetric electrodes, enables non-volatile storage in AFE HZO. Figure 1d demonstrates this built-in bias field engineering approach through a voltage-axis shift of the P–V curve.

According to the report by Pešić et al., the built-in bias field exhibited by WF engineering and fixed oxide charges can cause AFE hysteresis shift, enabling switching between polarized and non-polarized states in a nonvolatile manner7,12. We demonstrate the built-in bias field engineered Hf0.1Zr0.9O2 heterostructure, realized through PDA and asymmetric electrodes, enabling nonvolatile switching between upward polarization and non-polarization states at lower voltages. Figure 1e shows this built-in bias field effect through a voltage-axis offset of the P–V curve. As shown in Supplementary Fig. 4, the leakage J–V characteristics of the GNS/Hf0.1Zr0.9O2/W device are lower and exhibit greater asymmetry compared to that of the W/Hf0.1Zr0.9O2/W device. The energy band diagrams of the W/Hf0.1Zr0.9O2/W and GNS/Hf0.1Zr0.9O2/W devices are presented in Supplementary Fig. 5a and b. As illustrated in Fig. 1e, our built-in bias field-engineered Hf0.1Zr0.9O2 capacitor with GNS top electrode demonstrates voltage-controlled polarization switching: positive voltage pulse reconfigures the polycrystalline Hf0.1Zr0.9O2 matrix into a non-polar configuration, whereas negative pulse induces a polarized state. Remarkably, the pyroelectric response only appears in the polarized configuration due to its non-centrosymmetric crystal symmetry. This phase-dependent functionality enables selective photo-pyroelectric generation under instantaneous optical excitation—photon absorption in the GNS electrode induces rapid thermal transients within the polarized lattice, producing detectable photocurrent pulses through polarization-coupled pyroelectric conversion. Such opto-ferroelectric coupling enables nondestructive optical readout of programmed polarization states.

Figure 2a presents the P–V hysteresis loops of clamped post-metallization annealing (PMA) processed W/Hf0.1Zr0.9O2/W capacitor under different sweep amplitudes. The PMA-treated film exhibits an AFE-like behavior with double hysteresis loops, originating from reversible field-driven non-polar→polarized transitions30,33. Figure 2d shows current density-voltage (J-V) curves of PMA-processed W/Hf0.1Zr0.9O2/W device, revealing two switching/backswitching current pairs of AFE properties (labeled as I/I* and II/II*), where asterisks denote backswitching processes. Figure 2b exhibits AFE-like hysteresis and a small non-zero Pr at zero electric field in non-clamped PDA-processed W/Hf0.1Zr0.9O2/W device. Figure 2e exhibits a partial shift in J-V characteristics relative to Fig. 2d, demonstrating that the PDA process introduces built-in bias fields by modulating interfacial asymmetry34. The PDA-processed GNS/Hf0.1Zr0.9O2/W device shows a significant 2Pr value of ~30 μC cm−2, as shown in Fig. 2c. This value is much higher than the 2Pr value in HfO2-ZrO2 thin films with metal-ferroelectric-insulator-semiconductor (MFIS) structure24,26,27. P-V and J-V curves for PDA-processed Hf0.1Zr0.9O2 with Cr, Ni and Pt top electrodes are provided in Supplementary Fig. 6. Compared with traditional metal electrode capacitors, GNS electrode capacitors exhibit enhanced polarization values, which may be due to the van der Waals contact between the graphite electrode and Hf0.1Zr0.9O2 interface, as well as the chemically inert surface, where defects at the interface are relatively fewer35,36. Consistently, the GNS-electrode device shows the lowest leakage current among all tested samples (Supplementary Fig. 4), further confirming the reduced interfacial defect density at the van der Waals interface. The J–V curves in Fig. 2f reveal two notable FE-like polarization switching peaks. These effects originate from the electrode asymmetry37 and PDA-mediated interface modulation34 working together to create a substantial built-in bias field. The work function mismatch in asymmetric electrodes (W: 4.55 eV vs. GNS: 4.6–4.7 eV) directly establishes this built-in field38,39. In addition, we have directly measured the work function of our GNS using Kelvin Probe Force Microscopy (KPFM), which yields ~4.68 eV (Supplementary Fig. 7), in agreement with the literature. This mechanism is further evidenced by the pronounced coercive voltage (Vc) asymmetry observed in PDA-processed GNS/Hf0.1Zr0.9O2/W thin films, confirming the strong built-in electric field.

Furthermore, systematic measurements of P-V characteristics in PDA HfxZr1-xO2 and WF-engineered Hf0.1Zr0.9O2 films with GNS top electrodes reveal that PDA-processed Hf0.1Zr0.9O2 achieves maximum remanent polarization, outperforming WF-engineered counterparts as shown in Fig. 3a. In addition, PDA-processed Hf0.25Zr0.75O2 and ZrO2 devices achieve higher remanent polarization compared to WF-processed devices (Supplementary Fig. 8). Notably, our PDA method circumvents the electrode replacement step required in conventional WF engineering, simultaneously simplifying device fabrication and avoiding surface defects induced by Standard Cleaning 1 processes. Next, Positive-up-negative-down (PUND) measurements were performed to verify the reliable FE-like storage characteristics of the PDA GNS/Hf0.1Zr0.9O2/W capacitors. Figure 3b shows the input voltage (double pulse) and current response during PUND measurement of the PDA GNS/Hf0.1Zr0.9O2/W device. As expected, the current corresponding to the first positive/negative pulse is higher than that of the second positive/negative pulse, confirming significant polarization switching in the PDA Hf0.1Zr0.9O2 layer. The current generated by the first positive/negative pulse includes contributions from both polarization switching and non-switching currents (such as leakage and capacitive currents)40. In contrast, only non-polarization switching currents are observed during the second positive/negative pulse, as no polarization switching occurs at this stage.

As critical reliability parameters for nonvolatile memory applications, endurance and retention characteristics were characterized in the PDA GNS/Hf0.1Zr0.9O2/W capacitors (measurement scheme detailed in Supplementary Fig. 9). Figure 3c depicts the remanent polarization (Pr) evolution during bipolar cycling under 100 kHz bipolar cycling using 4 V triangular waveforms. The corresponding P–V and J–V curves are shown in Supplementary Fig. 10. Remarkably, stable cycling of 109 cycles was achieved, demonstrating wake-up-free operation and enhanced fatigue resistance. Supplementary Fig. 11 shows additional endurance measurements on three more devices under the same conditions, all demonstrating the same enhanced fatigue resistance. The remarkable endurance likely originates from polarization-state modulation between polar and nonpolar states, rather than full reversal of polarization, which is consistent with the mechanism proposed by Pešić et al. 7. Retention testing (Fig. 3d) confirms stable polarization states with extrapolated data retention exceeding 10 years, meeting industry requirements for NVM applications. At working temperatures of 353 K, the device also maintains good retention characteristics (supplementary Fig. 12).

Figure 3e displays polarization switching characteristics of PDA GNS/Hf0.1Zr0.9O2/W capacitor under varying write pulses. The device was initialized by a triangular pulse, and the last two pulses read the remaining polarization switched by the written pulse. Voltage-dependent intermediate states demonstrate precise control through bias amplitude modulation. To confirm consistency, we repeated each voltage pulse sequence 100 times, and measured the switchable polarization results for each state; as shown in Fig. 3f, PDA GNS/Hf0.1Zr0.9O2/W capacitor exhibits reliable consistency under conventional voltage control.

To probe the intrinsic pyroelectricity of the PDA GNS/Hf0.1Zr0.9O2/W device, Sharp-Garn measurements (TA = 1.8 K, T = 15 s; Methods) under zero-bias (Vbias = 0) conditions reveal voltage-controlled phase responses41,42. As shown in Fig. 4a, at −4 V poling (polarized state), a pure pyroelectric current density (~6 nA cm−2) emerges with near-ideal phase coherence (Φ ≈ 94°, theoretical limit 90°), yielding a giant pyroelectric coefficient p = −39.2 ± 0.5 μC m−2 K−1. This measured coefficient notably aligns with the commonly reported range (−30 to −70 μC m−2 K−1) for HfO2-based ferroelectric films19. The pyroelectric coefficient p quantifies current density generation per unit temperature change, and the negative sign confirms polarization decreases with heating (dP/dT < 0)43. At +4 V poling (non-polar state), the pyroelectric response decreases significantly, with only a small remaining value of −4.1 ± 0.4 μC m−2 K−1. This bipolar modulation evidences voltage-controlled polarization switching. Figure 4b shows hysteresis loops in pyroelectric coefficients versus voltage, matching Landau-Devonshire theory where p exhibit proportional dependence on both remnant polarization and relative permittivity19. In summary, the pyroelectric properties exhibited by Hf0.1Zr0.9O2 thin films enable non-destructive light detection by utilizing the material’s pyroelectric response and GNS light absorption.

The self-powered photoresponse was studied systematically. As shown in Fig. 4c, d, light pulses induce heat generation in the GNS, causing temperature spikes in Hf0.1Zr0.9O2 that reduce polarization (P → P - ΔP), thereby creating current density spikes (Jpy)23. When exposed to continuous light, the pyroelectric current vanishes as temperature stabilizes. Similarly, when the light is turned off, rapid cooling generates inverted current peaks (-Jpy). In both cases, the pyroelectric current density follows Jpy = p·dT/dt, and dT/dt is the temperature change rate from light absorption44. Reproducible testing using multiple illumination pulses showed no noticeable degradation in current density peaks, confirming the stability of the photo-pyroelectric current density generation (Supplementary Fig. 13). Additionally, the response times within a switching cycle were recorded at 17 ms, as shown in Supplementary Fig. 14. Control experiments with W and graphene top electrodes (Supplementary Fig. 15) showed similar P–V loops but no obvious photoresponse, confirming GNS’s specific light absorption enables the photo-thermal-polarization coupling required for pyroelectric charge generation. This effect requires simultaneous light variation and polarization dynamics—current only occurs when both light changes and polarization exist. To investigate this phenomenon further, the surface temperature change induced by pulsed-light illumination was simulated. The details of the simulation are provided in Supplementary Fig. 16 and related text (Supplementary Information).

The device’s self-powered response characteristics were tested at Vbias = 0 V under varying light power. As shown in Fig. 5a, current density peaks grew significantly from ~23 to 79 nA cm−2 as 475 nm light power increased from 0.5 to 2 mW cm−2. This power dependence comes from stronger temperature changes and faster heating/cooling rates under higher light intensity, which amplify polarization changes. Figure 5b displays the responsivity (R = Ipy/(A·P), where A is the effective device area (~23,000 μm2) and P is light intensity) under 475 nm illumination. The maximum value reaches ~46.2 μA W−1 across different power densities. The self-powered instantaneous response was systematically investigated at Vbias = 0 using 475, 530, 585, 635, 980, and 1550 nm light sources with same power densities (2 mW cm−2). The dynamic response shown in Fig. 5c, d reveals a wavelength-dependent response from 475 to 1550 nm, indicating varying photoactivity. The highest pyroelectric current density peaks (Jpy ≈ 79 nA cm−2) at 475 nm likely results from enhanced light absorption, consistent with the GNS and HZO absorption spectra in Supplementary Fig. 17. The van der Waals GNS electrode retains stronger remnant polarization than conventional semiconductor absorption layers, while avoiding complex lithography required by subwavelength metamaterials45. The broadband optical absorption properties of graphite suggest potential for wide-spectrum photodetection. This cost-effective configuration achieves superior photothermal conversion efficiency, presenting a viable alternative for optimizing photo-pyroelectric device performance.

In addition, transient current density measurements at zero bias showed how polarization states affect light response. As shown in Fig. 5e, f, when applying +1 V to +4 V pulses (10 μs), current density peaks decreased from ~79.1 to 5.5 nA cm−2 as the material phase changed from polar to non-polar. The polar state generates electricity through temperature-induced polarization changes (pyroelectric effect)23, while the non-polar state lacks this capability. Conversely, negative pulses (−1 V → −4 V) induce non-polar → polar state restoration with Jpy recovery to its initial ≈ 79 nA cm−2. Figure 5g demonstrates a FE-like loop in responsivity, where maximum R ≈ 39.5 μA W−1 emerges at −4 V (Hf0.1Zr0.9O2 upward polarized state), sharply contrasting with the R ≈ 2.8 μA W−1 minimum at +4 V (non-polar state). These test results are basically consistent with the pyroelectric response test results of voltage programming in Fig. 4b. These measurements demonstrate voltage-polarity switching of the photothermal-pyroelectric response, with positive pulses deactivating (OFF) and negative pulses activating (ON) the output. Supplementary Fig. 18 quantifies the ON/OFF states after 109 switching cycles, revealing <15% variation in both response amplitudes—consistent with the exceptional endurance shown in Fig. 3c. Our device achieves reconfigurable photo-pyroelectric control with >109 stable switches, outperforming existing systems (Supplementary Table S1). Notably, characterization of endurance over repeated voltage switching cycles is currently absent from the literature. This voltage-controlled photoresponse behavior enables non-destructive polarization readout, demonstrating potential for in-memory sensing and computing applications.

Methods
Sample preparation
The 40 nm-thick W bottom electrodes were deposited on the SiO2/Si substrates via sputtering. Hf0.1Zr0.9O2 (x=0.25, 0.1, 0) thin films with 8 nm thickness were subsequently grown by atomic layer deposition (ALD) at 230 °C. [(CH3)2N]4Hf (TEMAH), [(CH3)2N]4Zr (TEMAZ), and H2O were used as Hf precursor, Zr precursor, and oxygen source, respectively. The HfxZr1-xO2 films were processed through three distinct protocols: (1) For the PDA process, the HfxZr1-xO2 films underwent rapid thermal annealing (RTA) at 600 °C for 30 s in N2 ambient, then two distinct top electrode configurations were employed: mechanically exfoliated GNS were dry-transferred as top electrodes, whereas photolithography-patterned 40 nm sputtered W top electrodes (100×100 μm2) served as control samples; (2) For the PMA Hf0.1Zr0.9O2 film, 40 nm W top electrodes were sputter-deposited prior to RTA crystallization; (3) For the WF process, W top electrodes capping followed by the same RTA, then the W layer was etched away via Standard Cleaning 1 wet etching in a 50:2:1 H2O/H2O2/NH3 solution at 50 °C for 5 min, and finally the GNS were transferred onto the bare HfxZr1-xO2 film.

Details of GNS transfer: The dry transfer of GNS was performed on a dedicated two-dimensional material transfer station. Prior to the transfer, the target substrate was thoroughly cleaned by sequential ultrasonic cleaning in acetone, ethanol, and deionized water. Graphite nanosheets were prepared via mechanical exfoliation from a bulk graphite crystal using polymer tape, and transferred onto the PDMS surface. The GNS-loaded PDMS stamp was aligned and brought into contact with the substrate under optical microscopy. To facilitate GNS release, the PDMS was gradually pressed from one side against the substrate, allowing progressive contact formation, and then slowly peeled from the same edge to minimize bubble formation. Following transfer, the sample was immersed in acetone for 30 min to remove organic residues, followed by sequential rinsing with ethanol and deionized water. Finally, the sample was dried under a stream of nitrogen gas.

Microstructural characterization was performed using scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDX). Cross-sectional samples were prepared via focused ion beam (FIB, FEI Helios) milling, followed by high-resolution TEM analysis. TEM imaging confirmed the polycrystalline nature of the ferroelectric Hf0.1Zr0.9O2 layer. The HRTEM imaging was performed on a field emission transmission electron microscope operated at 200 kV (Talos F200i, Thermo Fisher Scientific). Aberration-corrected HAADF and iDPC imaging were performed on a double aberration-corrected scanning/transmission electron microscope operated at 300 kV (Themis Z, Thermo Fisher Scientific). For atomic-resolution STEM imaging, the convergence angle was set to 21.4 mrad under aberration-free conditions, with the DPC signal collected between 10 and 37 mrad and the HAADF signal collected from 39 to 200 mrad. Raman spectroscopy characterization was performed using a HORIBA HR Evolution Raman spectrometer with 532 nm laser excitation. Using Molecular Vista Photoinduced Force Microscopy (Kelvin Probe Force Microscopy mode), we measured the contact potential difference (CPD) between the GNS and a gold reference electrode.

Device characterization
Ferroelectric properties were evaluated using a Keithley 4200A-SCS parameter analyzer equipped with the 4225-PMU module. Polarization-voltage (P–V) hysteresis loops and current density-voltage (J–V) characteristics were measured at 1 kHz with ±4 V bipolar excitation. The endurance tests applied 4 V square-wave voltages at 100 kHz frequency, with the bottom electrode grounded throughout measurements.

Pyroelectric and photo-pyroelectric measurements
Pyroelectric measurements were carried out with the Sharp-Garn method under zero bias, applying sinusoidal thermal modulation41,42. The pyroelectric current was quantified using:

p = I A / (T A * A * 2πf) (1)

where I A is the measured current amplitude, Φ is the phase shift between the temperature and current signal, T A is the temperature amplitude, A is the capacitor area, and f is the temperature frequency. Hence, a phase shift of Φ = 90° represents a pure pyroelectric signal, and Φ = 0° is a non-pyroelectric signal. Keithley 4200A-SCS was used to measure the output current. The optical pulses were generated by a function generator (RIGOL DG1022Z) driving light-emitting diodes (λ = 475, 530, 585, 635, 980, 1550 nm). All light response data were acquired under zero bias voltage. The incident light intensity was measured by the light power meter (THORLABS). Visible absorption spectra were measured with a Filmetrics F40 thickness gauge.

Peer review rounds
[{"round": 1, "reviewer_comments": {"reviewer_1": "This manuscript presents an interesting and original contribution by integrating pyroelectric sensing with antiferroelectric (AFE) Hf0.1Zr0.9O2 memory, thereby achieving nondestructive optical readout in a nonvolatile memory system. The novelty lies in combining the intrinsic phase-transition properties of AFE-HZO with photo- pyroelectric functionality enabled by van der Waals GNS electrodes, which provides both memory storage and optical sensing capability in a unified device. The work demonstrates strong originality and conceptual advance in multifunctional memory design. In terms of integration, the proposed device successfully merges nonvolatile memory functionality (electrical polarization switching, retention, endurance) with sensing behavior (photo-pyroelectric readout and responsivity), offering a dual operation mode that bridges memory and optoelectronics. This multifunctional approach highlights potential for in-memory sensing and computing architectures. The experimental results are also comprehensive and convincing. The authors provide clear structural characterization (TEM, STEM, EDX) confirming material quality, robust electrical characterization (P-V hysteresis, J-V, PUND, retention, cycling), and extensive optoelectronic measurements (photo-pyroelectric response, responsivity across wavelengths, stability over repeated cycles). The combination of structural, electrical, and optical evidence makes the study well-rounded and complete. Nevertheless, despite these strengths, I have the following comments and suggestions that should be considered to further strengthen the manuscript: 1. In the Results section, the authors state that “0.294 nm lattice fringes correspond to the (111) planes of FE orthorhombic phases (Pca21),” whereas Fig. 1c appears to show lattice fringes of 0.296 nm. This small but non-negligible discrepancy should be clarified. In addition, since the lattice spacings of o-phase and t-phase HZO are very close, TEM lattice fringe analysis alone cannot unambiguously distinguish the two. Additional structural characterization (e.g., SAED, XRD, or Raman) would be needed to confirm the phase assignment. 2. In Fig. 1d, the P-V curve appears to exhibit a vertical shift rather than the expected horizontal offset typically associated with built-in bias fields arising from work-function mismatch. A vertical shift is more often related to interfacial charge injection, leakage contributions, or asymmetry in non-switching currents, rather than a pure built-in field effect. The authors are encouraged to clarify the underlying mechanism and, if possible, provide supporting evidence (e.g., leakage current separation, PUND verification, or interface charge analysis) to substantiate the claim that this behavior originates from the built-in bias. 3. The manuscript claims that the orthorhombic (o) ↔ tetragonal (t) phase transition in Hf0.1Zr0.9O2 can be realized solely by applying voltage pulses of opposite polarity, enabled by the built-in bias field and PDA treatment. I find this interpretation questionable. From a materials physics perspective, the stabilization of the o-phase in HfO2- based systems is generally attributed to dopants, film thickness, strain, and interface energy effects, rather than to the polarity of an applied electric field. Built-in bias fields or PDA are unlikely to induce a genuine crystallographic phase transformation between the o and t phases at room temperature. Instead, the reported results may more plausibly be explained by polarization switching or AFE-like dipole reordering, rather than a true structural o↔t phase transition. The evidence provided (shifted P-V loops and the presence/absence of pyroelectric response) does not unambiguously demonstrate structural phase conversion. In particular, the disappearance of pyroelectricity under positive poling could equally be due to compensation or suppression of polarization, rather than conversion to a centrosymmetric t-phase. I therefore recommend that the authors either provide more direct structural evidence for the claimed o↔t transition, or rephrase their description in terms of polarization state control rather than true phase switching. 4. The authors claim that the orthorhombic (o) ↔ tetragonal (t) phase transition in Hf0.1Zr0.9O2 can be reversibly achieved by applying voltage pulses of opposite polarity (positive pulses driving the material into the non-polar t-phase and negative pulses restoring the polar o-phase). This interpretation is used to explain the ON/OFF behavior of the pyroelectric response. However, this claim appears inconsistent with the endurance results reported in Fig. 3c. Specifically, if each +4 V/−4 V cycle indeed involved a large-scale crystallographic conversion between the o- and t-phases, such repeated structural transformations would be expected to introduce significant defect rearrangements and fatigue, making it highly unlikely to sustain stable remanent polarization over 109 cycles at 100 kHz without wake-up or degradation. The fact that robust endurance is observed under precisely these cycling conditions strongly suggests that the dominant mechanism is not full o↔t phase switching. A more plausible interpretation is that the applied bias modulates the polarization state (e.g., dipole reordering, AFE-like switching, or partial adjustment of o/t phase fractions) rather than inducing a complete crystallographic phase transition. The disappearance of pyroelectricity under positive poling may thus reflect polarization suppression or compensation, not a wholesale transformation to the centrosymmetric tetragonal phase. 5. The authors attribute the immediate stabilization of the o-phase after GNS transfer to the built-in bias field (from the GNS/W work function mismatch) combined with a defect-free van der Waals interface. However, the explanation that the built-in field alone can lower the free energy of the polar o-phase and thus favor its formation is not fully convincing. Typically, a built-in field manifests as a P–V loop shift rather than directly driving structural phase transformation. Please provide stronger justification (e.g., Landau–Devonshire analysis, DFT calculations, or literature evidence) that the estimated built-in field is sufficient to stabilize the o-phase. In addition, the relative contributions of the vdW interface (defect suppression) versus the built-in field should be clarified, and it should be explicitly stated whether the o-phase fraction increases already after PDA or only after GNS transfer. Furthermore, if work function mismatch is indeed the main driving factor, the authors should verify whether other asymmetric metal electrodes (with comparable or larger WF differences) produce the same effect. Finally, the claim of a “defect-free vdW interface” requires stronger evidence—can this be substantiated by direct interfacial characterization (e.g., STEM/EDX, XPS, or defect-sensitive electrical measurements) rather than inferred indirectly from device performance? 6. The manuscript demonstrates that different voltage pulses can program multiple polarization states (Fig. 3e–f), suggesting multilevel storage capability. However, the photo-pyroelectric readout mechanism appears to distinguish only between the polar o-phase (pyroelectric ON) and the non-polar t-phase (pyroelectric OFF), i.e., a binary readout. This discrepancy between multilevel electrical programmability and binary optical readout should be clarified. Could the authors comment on whether intermediate polarization states can be reliably distinguished optically, or whether the photo-pyroelectric approach is inherently limited to two-state detection? If only binary readout is possible, what are the implications for potential memory applications? 7. The reported optical readout time (~0.5 s illumination) is significantly slower than conventional electrical readout, which may limit its applicability. Please comment on whether faster optical readout is feasible. 8. The optical tests were limited to the visible spectrum (475–635 nm). For realistic applications, especially in the infrared or telecommunication wavelength ranges, further validation would be important. 9. The feasibility of mechanically transferring GNS electrodes in large-scale IC fabrication is unclear. The authors should discuss whether alternative integration methods or scalable electrode materials could achieve the same effect.", "reviewer_2": "[Noteworthy results] This work demonstrates an antiferroelectric (AFE)-like Hf₀.₁Zr₀.₉O₂ memory device with van der Waals graphite nanosheet (GNS) electrodes, achieving non-destructive optical readout via a photo-pyroelectric mechanism. The reported results include wake-up-free endurance exceeding 10⁹ cycles, 10-year retention, and reconfigurable photoresponse with wavelength dependence. These findings are significant because they address a key challenge in hafnia-based ferroelectrics —destructive readout—while introducing an optical interface compatible with photonic systems. [Significance and relation to the field] The integration of ferroelectric memory with optical readout is novel and could have broad impact in post-Moore computing, optoelectronic memory, and in-memory sensing. Compared with prior studies that relied on conventional metal electrodes or complex work-function engineering, the GNS-based approach is more fabrication-friendly and provides additional optical functionality. This originality makes the work potentially suitable for Nature Communications. [Soundness of conclusions and evidence] While the experimental demonstrations are compelling, several aspects of the interpretation require further substantiation before the claims can be considered fully supported: Electronic screening: In ultra-thin (7–8 nm) HZO films with metallic electrodes, strong charge screening would normally suppress measurable pyroelectric currents. The manuscript does not provide a quantitative explanation of how semi-metallic GNS contacts enable the reported response. Modeling or discussion of screening length, interfacial states, or band alignment would strengthen the mechanistic basis. DOE / multiphysics analysis: The reported photoresponse arises from coupled optical absorption, transient heating, and polarization change. However, the manuscript lacks Design of Experiments (DOE) analysis or multiphysics simulations (e.g., optical–thermal–electrical). Finite-element modeling of temperature rise and the expected pyroelectric current (Jpy = p·dT/dt) would help confirm that the observed signals originate from genuine pyroelectric processes rather than thermal leakage. Temperature dependence: AFE HZO is known to exhibit temperature-sensitive phase stability, often transitioning to FE-like states at elevated temperature. No temperature-dependent measurements (P–V, retention, or photoresponse) are provided. Such data would be crucial to assess robustness and practical device applicability. Reliability and statistics: The endurance data (>10⁹ cycles) are impressive, but error bars or statistical variation across multiple devices are not reported. Including device-to-device distributions would make the reliability claims more convincing. Control experiments: The W-electrode control confirms the necessity of GNS, but additional controls using semi-transparent electrodes such as ITO or graphene would clarify whether the response is uniquely enabled by GNS–HZO coupling or a more general optical absorption effect. [Methodology and reproducibility] The fabrication and measurement methods are described in reasonable detail. The inclusion of supplementary figures on process flow, absorption spectra, and endurance characteristics is helpful. However, some methodological clarifications are still needed: Details of GNS transfer and interfacial cleanliness should be expanded, as interface quality critically affects ferroelectric behavior. Sharp–Garn pyroelectric coefficient measurements should include uncertainties and comparison with prior reports. [Overall assessment] The manuscript presents an innovative and promising device concept, and the experimental results are noteworthy. However, before publication in Nature Communications, additional quantitative analysis of screening effects, DOE/multiphysics modeling, and temperature dependence is required to fully support the conclusions. Addressing these points would not only validate the claims but also significantly enhance the impact and scientific rigor of the work.", "reviewer_3": "This paper describes a new non-volatile memory made of an antiferroelectric, Hf₀.₁Zr₀.₉O₂. Common antiferroelectric materials suffer from depolarization and have no distinct, stable polarization state. Thus, antiferroelectric memory suffers from short data retention time and is not yet practical. Furthermore, antiferroelectric memory typically reads data using an electric pulse, while the reading operation itself disturbs the data storage state and becomes destructive. Finally, antiferroelectric materials are sensitive to processing conditions, and common processing technology may further disrupt the polarization state. The paper discusses new strategies to overcome these challenges. Namely, these strategies include: (1) establishing energy barriers in two polarization states with a built-in electric field; (2) engineering the built-in field by matching top and bottom contacts with different work functions, namely graphite and tungsten contacts; (3) avoiding processing-induced defects by realizing a clean van der Waals interface between the graphite contact and Hf₀.₁Zr₀.₉O₂; and (4) utilizing a new light-powered optical readout scheme by coupling the photo-thermal effects of the graphite contact with the pyroelectricity of Hf₀.₁Zr₀.₉O₂ antiferroelectrics. These strategies result in a sandwich structure of graphite–Hf₀.₁Zr₀.₉O₂–tungsten capacitor. With these strategies, the paper discusses the polarization characteristics and measures several key metrics of non-volatile random-access memory based on Hf₀.₁Zr₀.₉O₂ antiferroelectrics. This sandwich structure of graphite–Hf₀.₁Zr₀.₉O₂–tungsten shows a clear bi-stable state of polarization and no polarization. Furthermore, these two states convert into each other via a ±4 V electrical pulse signal. In other words, these ±4 V pulses perform the writing operation of the memory. Over repeated electrical pulses, the device current shows strong decay. The paper reveals that such decay indicates polarization switching and data storage. After the writing operation, the paper further evaluates the capability and reliability of data retention. Over 10⁹ test cycles, the device maintains significant polarization and shows strong fatigue resistance. In the time domain, the paper projects a data retention time of over ten years, an industry standard for practical devices. Finally, the paper discusses optical readout of the data state. The paper proposes that optical excitation heats the graphite electrode and the Hf₀.₁Zr₀.₉O₂ antiferroelectric, inducing a pyroelectric current. This pyroelectric current only appears with polarization; thus, the current serves as a sensitive fingerprint of the data state. The paper shows the pyroelectric current is robust across a wide range of the visible spectrum and under optical power densities from 0.5 mW/cm² to 2 mW/cm². Promisingly, the pyroelectric current also appears under zero bias; therefore, the readout is solely powered by optical excitation. Taken together, the paper addresses the challenges with this novel device design and an optically powered, non-destructive readout mechanism. This paper presents new device designs. The device shows clear bi-stable states, electrically programmable memory effects, and optical accessibility. The devices also exhibit excellent data retention time and strong robustness; all the measurements show promising results. In the meantime, I have several major comments on the rationale of the key idea and device design, as well as minor comments on device performance and measurement. I list all my comments below; I will happily evaluate this manuscript again once the authors discuss and address the concerns. Major comments: 1. The major element of this proposed device design is work function engineering. The paper claims to use graphite to establish a built-in potential and modify the energy landscape. In line 164, the paper claims the graphite nanosheet has a work function of 4.6–4.7 eV. The paper further cites works on the work function of carbon nanotubes. However, (1) carbon nanotubes and graphite nanosheets do not necessarily have the same work function, and (2) 2D nanosheets often show interface-dependent work functions and exotic phenomena such as Fermi-level pinning. I suggest the authors better support this claim by measuring the work function and barrier height of their device. 2. The paper also claims the graphite contact contributes to higher interfacial quality and higher nonzero remnant polarization Pᵣ (line 56, line 158). However, the paper hardly discusses any measurements on the interface. Since the interface consists of an ALD-grown thin film and a 20-nm-thick graphite layer, the exact interface quality is complex. Consider the following issues. (1) The graphite is very thick. Thick bulk graphite is likely to have sharp steps and form several-nm-wide air gaps when stacked on the antiferroelectric. In this sense, van der Waals interaction does not adequately describe the interface. (2) Even in regions without air gaps, how clean is the interface? The dry transfer process often results in many defects such as polymer contamination, trapped air bubbles, and gaps. I feel it is necessary to include these metrics when reporting the interface quality and quantifying the van der Waals interface. Currently, the interfacial quality remains unclear. 3. The paper reports two methods to induce a built-in electrical field: post-deposition annealing and asymmetric contacts. In particular, in Figure 2 and Supporting Figure 4, the devices with post-deposition annealing alone already show decent remnant polarization Pᵣ. The paper also mentions that annealing per se is more effective than work function engineering (line 171). How much does the graphite contact contribute to boosting the remnant polarization Pᵣ? Minor comments 1. In Figure 4(c), the paper discusses the time response of the pyroelectric current signal. Figure 4(c) shows a typical readout process lasting at least 0.1 second. Why is this process so slow? Which step is the rate-limiting step? I will also welcome a short discussion on potential plans to make the readout faster for practical devices. 2. In addition to the graphite–Hf₀.₁Zr₀.₉O₂–tungsten stack, the final device also has a 5 nm thick chromium layer on graphite. A 5 nm metal deposition on 2D nanosheets often forms islands instead of a continuous thin film, and the paper would benefit from a quick clarification. Furthermore, assuming a continuous thin film, how does this 5 nm thick chromium layer affect light absorption efficiency? 3. The paper uses excessive abbreviations, such as GNS, PMA, PDA, TE, BE, etc. These abbreviations significantly slow down and hinder understanding of the manuscript and are unnecessary. Please refrain from and remove non-standard abbreviations as much as possible."}, "author_response": "ResponsetoReviewer#1’scomments: This manuscript presents an interesting and original contribution by integrating pyroelectric sensingwithantiferroelectric(AFE)Hf0.1Zr0.9O2memory,therebyachievingnondestructive optical readout in a nonvolatile memory system. The novelty lies in combining the intrinsic phase-transition properties of AFE-HZO with photo- pyroelectric functionality enabled by van der Waals GNS electrodes, which provides both memory storage and optical sensing capability in a unified device. The work demonstrates strong originality and conceptual advanceinmultifunctionalmemorydesign. In terms of integration, the proposed device successfully merges nonvolatile memory functionality (electrical polarization switching, retention, endurance) with sensing behavior (photo-pyroelectric readout and responsivity), offering a dual operation mode that bridges memory and optoelectronics. This multifunctional approach highlights potential for in-memorysensingandcomputingarchitectures. The experimental results are also comprehensive and convincing. The authorsprovide clear structural characterization (TEM, STEM, EDX) confirming material quality, robust electrical characterization (P-V hysteresis, J-V, PUND, retention, cycling), and extensive optoelectronic measurements (photo-pyroelectric response, responsivityacrosswavelengths, stability over repeated cycles). The combination of structural,electrical, and optical evidence makesthestudywell-roundedandcomplete. Response:WesincerelythankReviewerforevaluatingour resultsas“interestingandoriginal contribution” and “…demonstrates strong originality and conceptual advance…”. Your encouragingremarksandvaluablesuggestionshavegreatlyhelpedusimproveourmanuscript. In particular, we highly appreciate your recommendation to reinterpret our results in terms of polarization modulation rather than an o-t phase transition, and we have adopted this perspective intherevision.Wehavealsocarefullyconsideredallofyourother commentsand have revised the manuscript accordingly. In the following, we address all comments point-to-point: Nevertheless, despite these strengths, I have the following comments and suggestions that shouldbeconsideredtofurtherstrengthenthemanuscript: 1. IntheResultssection,theauthorsstatethat“0.294nmlatticefringescorrespondtothe (111) planes of FE orthorhombic phases (Pca21),” whereas Fig. 1c appears to show lattice fringes of 0.296 nm. This small but non-negligible discrepancy should be clarified. In addition, since the lattice spacings of o-phase and t-phase HZO are very close, TEM lattice fringe analysis alone cannot unambiguously distinguish the two. Additionalstructuralcharacterization(e.g.,SAED,XRD,orRaman)wouldbe needed toconfirmthephaseassignment. Response:Wesincerelythankthereviewerforthisveryimportantcomment.Thediscrepancy between0.294nm inthe text and0.296nm inFig.1c arose from ourtypo errorinFig. 1cand the correct value should be 0.294nm. We fully agree that distinguishing the o-phase and t-phases of HZO based solely on the [110] lattice spacing is challenging due to their similar values. Therefore, in the revised manuscript, we have followed Reviewer’s advice and removed the statement “0.294 nm lattice fringes correspond to the (111) planes of FE orthorhombic phases (Pca2 space group)30-32”. [Wenote that although some previous reports have tentatively assigned the o-phase based on lattice spacing, we agree with the Reviewer that this criterion alone is not fully convincing.Accordingly, we have revised the manuscript following the Reviewer’s suggestion. In addition, we performed further STEM observations to obtain more definitive evidence for the presence of the o-phase in our samples, as demonstratedbelow.] To examine whether the o-phase of Hf Zr O exists in our samples, we therefore 0.1 0.9 2 conducted atomic-resolution STEM imaging using an aberration corrected electron microscope(Themis Z,ThermoFisher Scientific,fittedwithCEOS SCORRprobe corrector). The microscope was operated at 300 kV and the probe forming semi-angle was set to 21.4 mrad to achieve sub- Angstrom spatial resolution. We employed complementary STEM techniques, including High-angle annular dark-field (HAADF) and integrated Differential Phase Contrast (iDPC) imaging, the latter being highly sensitive to light elements.As shown in the Fig.R1(a) (revised Fig. 1c, HAADF image) and Fig.R1(b) (revised Fig. 1d, iDPC image),thenanocrystallinecanbedirectlyidentifiedasO-phaseHf Zr O viewedalongthe 0.1 0.9 2 [010]zone axis.Inparticular,theiDPCimage clearlyreveals that halfoftheoxygencolumns deviate from the central position of the four nearest Hf/Zr atoms—a typical characteristic of theO-phaseviewedalongthe[010]zoneaxis[1-4].Theseresultsprovidestrongevidencefor thepresenceoftheo-phaseinoursamples. For consistency with Fig.1d, we have also replaced the previous Fig.1c with a more representativeatomic-resolutionHAADF-STEMimage(Fig.R1(a),revisedFig.1c). [1] Park, M.H. et al.FerroelectricityandAntiferroelectricityof DopedThinHfO2-Based Films.Adv.Mater.27,1811-1831(2015). [2] Cheng, Y. et al. Reversible transition between the polar and antipolar phases and its implicationsforwake-upandfatigueinHfO2-basedferroelectricthinfilm.Nat.Commun.13, 645(2022). [3] Zheng, Y. et al. Influence of interface on the domain polarization orientation in ferroelectricHf0.5Zr0.5O2thinfilms.Ceram.Int.50,51894-51900(2024). [4] Li, X. et al. Polarization Switching and Correlated Phase Transitions in Fluorite-StructureZrO2Nanocrystals.Adv.Mater.35,2207736(2023). Fig. R1. (a) HAADF image. Hf/Zr atoms visible only. (revised Fig. 1c) (b) iDPC image. Hf/ZrandOxygenatomsvisible.(revisedFig.1c,d) 2. In Fig. 1d, the P-V curve appears to exhibit a vertical shift rather than the expected horizontal offset typically associated with built-in bias fields arising from work- functionmismatch.Averticalshiftismoreoftenrelatedtointerfacialchargeinjection, leakage contributions, or asymmetry in non-switching currents, rather than a pure built-in field effect. The authors are encouraged to clarify the underlying mechanism and, if possible, provide supporting evidence (e.g., leakage current separation, PUND verification, or interface charge analysis) to substantiate the claim that this behavior originatesfromthebuilt-inbias. Response: We sincerely appreciate the reviewer’s insightful comment. We agree that vertical shift indeed may occur in our samples due to interfacial charge injection, leakage contributions or non-switching current asymmetry. We apologize for not providing sufficient explanation about why we conclude the horizontal shift to be dominant in our samples and why we believe the vertical shift plays a minor role (less than 5%). In the following,wedescribeinmoredetail: (1) The presence of horizontal asymmetry can be seen from Fig. R2(a), in which the light blue curve shows the raw data of J-V curve. This J-V curve exempts from the integration operation (unlike P-V curve) and hence the horizontal shift is less affected by the leakage or non-switching current vertical asymmetry. It can be seen that the peak under positive bias appears at ~+3.3V, while the peak under negative bias shows upat ~ -2.7V.This implies that the built-inbias is apparentlyimportant, although little informationisprovidedtotheverticalshift. (2) The leakage current measurements on GNS/HZO/W samples (red curve in Fig.R2b) showsthatstrongasymmetryofdip-positionsinthepositiveandnegative scans,unlike thenearlysymmetrydipfeaturesinW/HZO/W.Inaddition,theleakagecurrentdensity in GNS/HZO/W sample (@ ) is about 3 orders of magnitude lower than that in W/HZO/W (light blue curve in Fig.R2b), implying that the leakage current in ±2.5 GNS/HZO/Wplayslittlerole. (3) PUND measurements have been done (Fig.2b in our manuscript, and Fig.R2c in this reply) and the non-switching current densities (U and D in Fig. R2c) display only minor asymmetry. The J-V curve corrected by PUND (light blue in Fig. R2d) shows similarhorizontal asymmetryas in Fig.R2a; andthe P-V loop correctedby PUND (red in Fig. R2d) shows negligible vertical offset. To verify this conclusion independently, Fig.R2e shows the P-V loop measured using a double positive triangular voltage waveform (corresponding to the “PU” sequence of the PUND test), from which interceptofUintegrationisevaluatedtobe~5%ofPintegration.Theseresultsindicate that vertical shift due to interfacial charge injection, leakage contributions, or non-switchingcurrentsplaysonlyaminimalrole. (4) To more clearly demonstrate the built-in field effect, we fabricated additional devices using Pt (Φ ≈ 5.65 eV) as the top electrode, which provides a larger work-function difference relative toW.In the Pt/Hf Zr O /W device,boththe P-V (Fig. R3(a)) and 0.1 0.9 2 currentdensity peaks inthe J-V (Fig. R3(b)) characteristics shiftconsistently alongthe voltage axis toward the right, directly evidencing the built-in bias. Therefore, in the revised manuscript, we have replaced the original P-V curve in Fig. 1d with the P-V dataof thePt-baseddevice (Fig.R3(a),revisedFig. 1e) tomore explicitlyillustratethe built-infieldeffect. Fig. R2. (a) P-V hysteresis loops and J-V switching characteristics PDA-processed GNS/Hf Zr O /W sample. (b) The leakage currents of Post-deposition annealing 0.1 0.9 2 devices with different top electrodes. (c) The time-domain voltage and current density waveformsinthePUNDmeasurementofPDA-processedGNS/Hf Zr O /Wsample.(d) 0.1 0.9 2 ThecorrectedP-Vcharacteristics,whichwasobtainedfromthePUNDmeasurementin(c). (e)P-Vloopcorrespondingtothe “PU” sequenceofthePUNDtest. Fig. R3. Built-in bias field-induced the (a) P-V and (b) current density peaks in the I-V curveshiftinAFEcapacitor. In summary, we believe that the above results support a reliable conclusion that the horizontal shift dominates the behavior of our devices. Moreover, the photo-pyroelectric resultsshowninFig.4cannotbe self-consistentlyexplainedifoneassumesthat avertical shift, rather than the horizontal shift induced by the built-in bias, is the dominant mechanism. 3. The manuscript claims that the orthorhombic (o) ↔ tetragonal (t) phase transition in Hf0.1Zr0.9O2 can be realized solely by applying voltage pulses of opposite polarity, enabled by the built-in bias field and PDA treatment. I find this interpretation questionable. Froma materials physics perspective, thestabilizationof the o-phase inHfO2- based systems is generally attributed to dopants, film thickness, strain, and interface energy effects, rather than to the polarity of an applied electric field. Built-in bias fields or PDAare unlikely to induce a genuine crystallographic phase transformation between the o and t phases at room temperature. Instead, the reported results may more plausiblybeexplainedbypolarizationswitchingorAFE-likedipolereordering,rather thanatruestructuralo↔tphasetransition. The evidence provided (shifted P-V loops and the presence/absence of pyroelectric response) does not unambiguously demonstrate structural phase conversion. In particular, the disappearance of pyroelectricity under positive poling could equally be due to compensation or suppression of polarization, rather than conversion to a centrosymmetric t-phase. I therefore recommend that the authors either provide more direct structural evidence for the claimed o↔t transition, or rephrase their description intermsofpolarizationstatecontrolratherthantruephaseswitching. Response: We sincerely thank the reviewer for this thorough and insightful comment. In our initial submission, we referred to previous literature (IEEE Sens. J., 2024, 24, 8) that associated the transition between polar and non-polar states in antiferroelectric memory devices with the t-o phase transformation. However, following your valuable suggestion and our subsequent re-evaluation, we have revised our interpretation to focus on polarization-state modulation rather than structural phase switching. This updated framework is consistent with the Landau-Devonshire theory and prior studies (Adv. Funct. Mater. 2016, 26, 7486-7494), where the built-in bias field modifies the free-energy landscape and enables switching between polarized and non-polarized configurations without requiring a full crystallographic transformation. We also note that a recent study (Adv. Mater. 35, 2207736 (2023)) reported that “polarization switching is strongly correlated with Zr-O displacement in reversible martensitic transformation between monoclinic and orthorhombic phases and two-step tetrahedral-to-orthorhombic phase transition”,basedonin-situSTEMobservation.Buildingonthisresultandconsideringthat our iDPC observations (Fig. R1) confirm the presence of the o-phase in our samples, we surmise that a similar t-o phase transitionmay occur inour case.However, since our iDPC (STEM) measurements were not performed in situ, and to maintain scientific rigor, we follow the Reviewer’s advice to conservatively describe our observation as a polar-nonpolar transition rather than a t-o phase transition, so as to avoid over-interpretationorpotentialmisunderstandingbyreaders. RevisedMechanismDescription: All mentions of the “o-t phase transition” have been replaced by “polar/non-polar transition,” andthe correspondingannotationsinFigs.1e,1f,5e,and5f have beenupdated accordingly. Specifically:(1)Positive voltagepulsesinduceanon-polar(pyroelectricOFF) state; (2) Negative voltage pulses restore the polarized (pyroelectric ON) state. The observed nonvolatile behavior therefore arises from voltage-controlled polarization-state modulation,consistentwiththeexcellentenduranceandabsenceofwake-upeffects. 4. The authors claim that the orthorhombic (o) ↔ tetragonal (t) phase transition in Hf0.1Zr0.9O2 can be reversibly achieved by applying voltage pulses of opposite polarity (positive pulses driving the material into the non-polar t-phase and negative pulses restoringthe polar o-phase).This interpretation is used toexplainthe ON/OFF behavior of the pyroelectric response. However, this claim appears inconsistent with theenduranceresultsreportedinFig.3c.Specifically,ifeach+4V/−4Vcycleindeed involved a large-scale crystallographic conversion between the o- and t-phases, such repeated structural transformations would be expected to introduce significant defect rearrangements and fatigue, making it highly unlikely to sustain stable remanent polarizationover109cyclesat100kHzwithoutwake-up or degradation.The fact that robust endurance is observed under precisely these cycling conditions strongly suggeststhatthedominantmechanismisnotfullo↔tphaseswitching. A more plausible interpretation is that the applied bias modulates the polarizationstate (e.g., dipole reordering,AFE-like switching, or partial adjustment of o/t phasefractions)ratherthaninducinga completecrystallographicphasetransition. The disappearance of pyroelectricity under positive poling may thus reflect polarization suppression or compensation, not a wholesale transformation to the centrosymmetrictetragonalphase. Response: We sincerely thank the reviewer for this insightful and important comment. Although our additional iDPC (STEM) measurements confirmed the existence of o-phase, we agree with Reviewer that complete crystallographic phase transition is difficult to occur and, more likely, partial adjustment of o/t phase fractions, as proposed byReviewer. Recent studies (e.g., Adv. Mater. 35, 2207736 (2023)) have shown that the t-o activation involves primarily oxygen displacement within a nearly preserved Hf/Zr lattice framework. Therefore, even if local o-t conversion occurs, the structural rearrangement is expectedtobesubtle,consistentwiththeexcellentenduranceobservedinourdevices. Following the reviewer’s suggestion, we now describe the switching process as polarization-state modulation (rather than o-t phase transition). As detailed in our response to Comment 3, the built-in bias originating from the GNS/W work function difference further modulates the potential landscape, preferentially stabilizing one polarization orientation and thereby enabling the observed nonvolatile behavior. This interpretation is fully consistent with the device’s excellent endurance performance. In the revised manuscript, we also mentioned the above possible mechanisms for the robust endurance in our devices. We greatly appreciate the reviewer’s constructive guidance, which has significantlystrengthenedthephysicalconsistencyandclarityofourinterpretation. 5. The authors attribute the immediate stabilization of the o-phase after GNS transfer to the built-in bias field (from the GNS/W work function mismatch) combined with a defect-free van der Waals interface. However, the explanation that the built-in field alonecanlowerthefreeenergyofthepolaro-phaseandthusfavoritsformationisnot fully convincing. Typically, a built-in field manifests as a P–V loop shift rather than directly driving structural phase transformation. Please provide stronger justification (e.g., Landau–Devonshire analysis, DFT calculations, or literature evidence) that the estimated built-in field is sufficient to stabilize the o-phase. In addition, the relative contributionsofthevdWinterface(defectsuppression)versusthebuilt-infieldshould be clarified, and it should be explicitly stated whether the o-phase fraction increases alreadyafterPDAoronlyafterGNStransfer. Furthermore, if work function mismatch is indeed the main driving factor, the authors should verify whether other asymmetric metal electrodes (with comparable or largerWFdifferences)producethesameeffect. Finally, the claim of a “defect-free vdW interface” requires stronger evidence—can this be substantiated by direct interfacial characterization (e.g., STEM/EDX, XPS, or defect-sensitive electrical measurements) rather than inferred indirectlyfromdeviceperformance? Response: We sincerely thank the reviewer for these insightful and constructive comments. As described inour reply toprevious comments, our iDPC/STEM measurements confirm the presence of o-phase. On the other hand, structural phase transformation can take place under sufficient built-in bias but requires additional verifications.Weaddress this question as in the following: (1) Required built-in bias: According to the Landau-Devonshire calculation as presented in Adv. Funct. Mater. 2016, 26, 7486-7494, the required built-in field is about 0.7 MV/cm , therefore the required built-in bias is 0.7 MV/cm 8 nm 0.56 V. In the case of GNS/HZO/W, the extracted value is about 0.7 V, which is sufficiently large to meet this × ≅ requirement. The built-in bias in our devices was estimated from the shift of coercive voltageshift,,followingthemethodreportedinAdv.Funct.Mater.2025,35,2414187.The built-infieldoriginatesfromboththePDAprocess(Adv.Funct.Mater.2025,35,2414187) andthework-functiondifferencebetweenasymmetricelectrodes(Adv.Funct.Mater.2016, 26,7486-7494). (2) In-situinvestigationsonthepolarizationswitchingandphasetransitionsinthesameZrO 2 nanocrystals (Adv. Mater. 35, 2207736 (2023)) found that polarization switching is strongly correlated with Zr–O displacement in reversible martensitic transformation between monoclinic and orthorhombic phases and two-step tetrahedral-to-orthorhombic phase transition. From this result, we surmise that the fraction of o-phase may change due tothebuilt-inbiaswhichregulatesthepolar-nonpolarstates. (3) The vdW interface and built-in field act synergistically. The vdW interface effectively suppresses defect-assisted relaxation, leading to lower leakage current (Fig.R3b, Fig.R5c) and enhanced polarization retention. Meanwhile, the built-in bias arising from the work function difference betweenGNS andWshifts the P–Vcharacteristics alongthe fieldaxis and promotes a preferred polarization orientation. This cooperative effect explains the emergence of nonvolatile polarization. HZO thin films are typically amorphous in the as-deposited state and require annealing for crystallization into the o/t phases (Adv. Electron. Mater. 2018, 4, 1800091; Adv. Mater. 2015, 27, 1811–1831). We therefore attribute the formation of the crystalline phases primarily to the PDAprocess.After GNS transfer, the built-in bias field and the high-quality vdW interface modulate and stabilize thepolarizationconfigurationwithinthesepre-existingcrystallinephases. (4) Verification using other asymmetric electrodes. To further confirm that the observed effect originates from the work function mismatch, we performed additional experiments using Pt as the top electrode (Φ ≈ 5.65 eV), which produces a larger work function differencerelativetoW.AsshowninFig.R4(a,b)(nowincludedasSupplementaryFig.6), the Pt/Hf Zr O /W device exhibits a similar bias-induced stabilization of the 0.1 0.9 2 polarization state, confirming that the built-in bias associated with work function differenceplaysakeyrole. (5) Clarification on “defect-free” vdW interface and supporting evidence. We would like to apologizefortheuncleardescriptioninouroldversionbutwanttoclarifythatourclaimis notthatthevdWinterfaceisentirely“defect-free,”butratherthatitexhibitsasignificantly reduced defect density compared to conventional metal interfaces which bombard effect during metal deposition (e.g., via magneto sputtering) affects the interfacial quality. Layer transfer with atomically flat GNS, on the other hand, does not have this issue. Indeed, our EDX results (Supplementary Fig.2) show abrupt profiles (e.g., Zr) which suggest negligible interlayer mixing. Besides, we expect that globally the leakage current can reflect the interfacial quality since interfacial intermixing can degrade the device performanceandcauselargeleakagecurrentdensity.InFig.R4(c),onecanindeedseethat the GNS-electrode device exhibits the lowest leakage current density among all tested samples. In summary, the PDA process determines the formation of crystalline phases, while the subsequent GNS transfer introduces a built-in bias and a reduced-defect vdW interface that jointly stabilize the polarization state and suppress defect-mediated relaxation. The confirmationusingPt electrodes further supports the conclusionthat built-in bias engineering governstheobservednonvolatilepolarizationbehavior. Fig. R4. (a) P-V hysteresis loops and (b) J-V switching characteristics PDA-processed Pt/Hf Zr O /W sample. (Supplementary Fig. 6 c, f) (c) The leakage currents of 0.1 0.9 2 Post-depositionannealingdeviceswithdifferenttopelectrodes.(SupplementaryFig.4) 6. The manuscript demonstrates that different voltage pulses can program multiple polarization states (Fig. 3e–f), suggesting multilevel storage capability. However, the photo-pyroelectric readout mechanism appears to distinguish only between the polar o-phase (pyroelectric ON) and the non-polar t-phase (pyroelectric OFF), i.e., a binary readout. This discrepancy between multilevel electrical programmability and binary optical readout should be clarified. Could the authors comment on whether intermediate polarization states can be reliably distinguished optically, or whether the photo-pyroelectricapproachis inherentlylimitedtotwo-statedetection? If only binary readoutispossible,whataretheimplicationsforpotentialmemoryapplications? Response: We sincerely thank the reviewer for raising this important and thoughtful point regarding the relationship between multilevel electrical programmability and the readout capability of our photo-pyroelectric method. We fully agree that this distinction is crucial for evaluating the potential of our device in memory applications, and we appreciate the opportunitytoclarifyit. As mentioned in our revised interpretation (now framed in terms of polarization-state modulation rather than a structural phase transition), the “ON” and “OFF” states are more accurately described as the presence or absence of macroscopic remanent polarization. Importantly, the magnitude of the pyroelectric current is directly proportional to the magnitude of this remanent polarization. Therefore, our photo-pyroelectric readout is not inherently limited to binary detection. In fact, intermediate polarization states can also be reliably distinguished optically, as demonstrated by two key experimental results in our manuscript: 1. Figure 4b shows the measured pyroelectric coefficient as a function of the programming voltage amplitude. The data exhibit a continuous and monotonic evolution of the coefficient, corresponding directly to a continuous range of programmable remanent polarization states. This clearly demonstrates that the readout method can resolve more than twodiscretelevels. 2. Figure 5e further provides direct evidence through photocurrent measurements from devices programmed with voltage pulses of different amplitudes. The resulting photocurrent signals display multiple, distinct, and stable levels, confirming that the intermediate polarization states are not only electrically programmable but also optically readable in an analogfashion. In summary, while the binary “ON/OFF” terminology is convenient for describing the twosaturated polarizationstates, our photo-pyroelectricapproachis capable of distinguishing multiple intermediate states, thereby enabling multilevel optical readout consistent with the electricallyprogrammablepolarizationlevels. 7. The reported optical readout time (~0.5 s illumination) is significantly slower than conventional electrical readout, which may limit its applicability. Please comment on whetherfasteropticalreadoutisfeasible. Response:Wesincerelythankthereviewerforraisingthisimportantconcernregardingthe reported optical readout time (~0.5 s). This relatively slow response was limited by the electrical measurement bandwidth (instrumentation and device RC time constant) rather than the intrinsic speed of the device. The detected optical signal is a transient pulse that occurs only at the light-on and light-off edges; therefore, the intrinsic readout process can, inprinciple,bemuchfaster. To verify this, we performed additional measurements using a faster pulsed optical excitation (with higher illumination intensity) and a higher-bandwidth electrical setup, increasing the optical modulation frequency while keeping the same device structure. The transient current pulses (Fig. R5) accurately followed the faster illumination sequence without distortionand the rise time is at leastquicker than~17ms (whichis still limited by the sampling rate of the electrical instrument, Keithley 4200). This confirms that faster optical readout is indeed feasible.These results indicate that the readout speed is primarily limited by the measurement configuration and can be further improved through optimizationofcircuitbandwidth. Fig. R5. Faster optical readout verified by transient current response under higher illuminationandbandwidthconditions.(SupplementaryFig.14) 8. The optical tests were limited to the visible spectrum (475–635 nm). For realistic applications, especially in the infrared or telecommunication wavelength ranges, furthervalidationwouldbeimportant. Response: We sincerely thank the reviewer for this valuable comment. Validating device performance in the infrared and telecommunication wavelength ranges is highly pertinent for assessing its practical applicability. In response, we have conducted additional experiments (Fig. R6) using two representative infrared wavelengths: 980 nm (commonly employed for pumping sources and infrared illumination) and 1550 nm (the central wavelengthusedinfiber-opticcommunications).Thenewresults,nowincorporatedinFig. 5c,dof the revised manuscript, clearly demonstrate that our device exhibits a photothermal response at both wavelengths. As explained in the manuscript, the device operation relies on the broadband photothermal conversion capability of graphite, and is therefore inherentlybroadband,extendingnaturallyintotheinfraredandtelecommunicationregimes. Fig. R6. Photo-pyroelectric current density under different laser wavelengths at the same lightintensity.(Fig.5c,d) 9. The feasibility of mechanically transferring GNS electrodes in large-scale IC fabrication is unclear. The authors should discuss whether alternative integration methods or scalable electrode materials could achieve the same effect. Response: We sincerely thank the reviewer for raising this important point regarding the scalability of mechanically transferred graphite electrodes. We fully agree that while the mechanical transfer method is effective for proof-of-concept demonstrations, it presents challenges for large-scale IC manufacturing. To address these scalability concerns, future work could explore wafer-scale chemical vapor deposition (CVD) growth (e.g., Science 344, 286 (2014); Nature Materials 21, 740 (2022)) of graphite followed by standard photolithographic patterning, or adopt metal-assisted or polymer-supported transfer techniques to enhance throughput and uniformity. In addition, scalable alternatives such as the macroscopic assembly of graphene nanofilms or integration of graphite-based electrodes withinback-end-of-line (BEOL) processes through advanced packaging approaches may also offer promising routes. Overall, our present study should be regarded as a proof-of-concept thatestablishesaclearperformancebenchmarkandprovidesguidanceforthedevelopmentof next-generation,manufacturableintegrationstrategies. ResponsetoReviewer#2’scomments: [Noteworthyresults] This work demonstrates an antiferroelectric (AFE)-like Hf₀.₁Zr₀.₉O₂ memory device with van derWaals graphite nanosheet (GNS) electrodes, achievingnon-destructive optical readoutvia a photo-pyroelectric mechanism. The reported results include wake-up-free endurance exceeding 10⁹ cycles, 10-year retention, and reconfigurable photoresponse with wavelength dependence. These findings are significant because they address a key challenge in hafnia-based ferroelectrics—destructive readout—while introducing an optical interface compatiblewithphotonicsystems. Response: We sincerely thank the reviewer for carefully reviewing our work and evaluating ourfindingtobesignificant. [Significanceandrelationtothefield] The integration of ferroelectric memory with optical readout is novel and could have broad impact inpost-Moorecomputing, optoelectronic memory,andin-memory sensing. Compared with prior studies that relied on conventional metal electrodes or complex work-function engineering, the GNS-based approach is more fabrication-friendly and provides additional optical functionality. This originality makes the work potentially suitable for Nature Communications. Response:Wethankthereviewerverymuchforcommentingourworktobenovelandcould have broad impact, also judging the originality of our work makes the work potentially suitableforNatureCommunication. [Soundnessofconclusionsandevidence] While the experimental demonstrations are compelling, several aspects of the interpretation requirefurthersubstantiationbeforetheclaimscanbeconsideredfullysupported: Electronic screening: In ultra-thin (7–8 nm) HZO films with metallic electrodes, strong charge screening would normally suppress measurable pyroelectric currents. The manuscript does not provide a quantitative explanation of how semi-metallic GNS contacts enable the reported response. Modeling or discussion of screening length, interfacial states, or band alignmentwouldstrengthenthemechanisticbasis. Response: We sincerely thank the reviewer for the critical comments and for the suggestion. The following provides a quantitative discussion of the screening effect and the role of semi-metallicgraphene(GNS)contacts: Whenaferroelectricmaterialispolarizedbyanexternalelectricfield,thesurfacecharges resulting from ferroelectric dipoles induce a redistribution of free carriers within the adjacent electrodes. These redistributed carriers act as screening charges, however, that ideal screening—where the compensating charge layer has zero thickness—is generally not achievable in practice (see Junquera & Ghosez, Nature 422, 506 (2003); and 19th Non-VolatileMemoryTechnologySymposium(NVMTS),Durham,NC,USA,2019,pp.1-8). The screening lengths (l ) for graphite and tungsten (W) to be approximately 1.2 nm (2008 s Appl. Phys. Express 1 034007) and 0.067 nm (Small 2024, 20, 2305271), respectively. The longer screening length in semi-metallic graphite implies less perfect screening compared to conventional metals. To quantitatively describe the screening strength, we adopt the standard expressionforthedepolarizationfield(J.Appl.Phys.44,3379–3385(1973)): P 2ε d FE FE E =- ( dep ε ε 2ε d ε l 0 FE FE FE s s / ) where P is the ferroelectric polarization surface/charg+e, d/ is the ferroelectric thickness, FE ε and ε is the relative permittivity of the ferroelectric and electrode respectively. This FE s relation explicitly shows that a thinner ferroelectric or a longer electrode screening length leads to a larger depolarization field. Since the depolarization field is directly proportional to the uncompensated polarization charge, this formulation also reflects the efficiency of charge screening at the electrode/ferroelectric interface. Therefore, the incomplete screening behavior of graphite allows a detectable pyroelectric current to persist despite the ultrathin natureof the HZO film.Wehave addedthis discussionandthecitedreferences tothe revised manuscript/SI to clarify why semi-metallic GNS electrodes can still enable measurable pyroelectriccurrentsinourthinHZOdevices. To better illustrate the built-in bias field within the capacitor stack, we have provided a band diagram under zero bias (see Fig. R7, Supplementary Fig. 5), based on the assumption that HZO is fully insulating and free of space charge regions. For the GNS/HZO/W sample, when the HZO is in its non-polar state, a negative internal bias relative to the grounded bottom electrode is present. When the HZO is up-polarized, the depolarization field is reduced—orevenreversed—resultinginanopposinginternalpolarizationfield.Thisdiagram hasbeenaddedtotheSupplementaryInformation. Fig.R7.Energybanddiagramof(a)W/HZO/Wand(b)GNS/HZO/Wdevicesatnon-polar andpolarstates.(SupplementaryFig.5) DOE / multiphysics analysis: The reported photoresponse arises from coupled optical absorption, transient heating, and polarization change. However, the manuscript lacks Design of Experiments (DOE) analysis or multiphysics simulations (e.g., optical–thermal–electrical). Finite-element modeling of temperature rise and the expected pyroelectric current (Jpy = p·dT/dt) would help confirm that the observed signals originate fromgenuinepyroelectricprocessesratherthanthermalleakage. Response: We sincerely thank the reviewer for this insightful and important comment.As showninFig.5a,thetransientnatureof the photocurrent—appearingonlyatthe risingand fallingedges of the light pulse—is a well-established signature of pyroelectric behavior, as it depends on the temperature rate of change (dT/dt) rather than the absolute temperature (whichwouldinsteadsuggestthermoelectricorthermalleakageeffects). To further substantiate this interpretation, we have performed finite-element simulations using COMSOL Multiphysics to analyze the coupled optical-thermal response of the multilayer structure (GNS/Hf Zr O /W). In the simulation, Hf Zr O was approximated 0.1 0.9 2 0.1 0.9 2 as ZrO .Alaser powerdensityof 2mW/cm2 with60%absorptionat thegraphite surface was 2 appliedasarectangularpulsewith1µsrisetime.ThebottomWelectrodewasheldatafixed temperature of 293.15 K, while radiative losses were considered at the other boundaries. Interfacial thermal resistances (approximately 5·10-6K·m2/W) were incorporated between layers.Therefore,thethermalpropertiesofthematerialsarecharacterizedasfollows:  ZrO 2 : thermal conductivity (1.67 W/(m·K)), heat capacity (455.21 J/(kg·K)), density (5560kg/m³)  graphite: thermal conductivity (129 W/(m·K)), heat capacity (709.88 J/(kg·K)), density(2270kg/m³) W: thermal conductivity (178 W/(m·K)), heat capacity (132 J/(kg·K)), density  (19,250kg/m³) Aboveparametersaretakenfrom[HandbookofCarbon,Graphite,Diamond,andFullerenes: Properties, Processing, and Applications (Noyes Publications, 1993); Thermodynamic Properties of Elements and Oxides (US Bureau of Mines, 1982); CRC Materials Science and EngineeringHandbook3rdedn(CRCPress,2000)]. The simulated temperature change rate (dT/dt) across the ZrO layer (see Fig. R8, 2 Supplementary Fig. 16) exhibits sharp transients that are consistent with the experimentally observedphotocurrent pulses.These temperature variations cangenerate a noticeable current. In contrast to thermally activated leakage, which would produce a quasi-steady current under constant illumination, our simulation yields only transient responses associated with the temperature rate of change. This is fully consistent with the experimental observations, confirming that the measured photoresponse originates from a genuine pyroelectric process ratherthanthermalleakage. Fig. R8. (a) Simulated schematic view of simulation domain with material layers. (b) The transient temperature profile for a large number of cycles, shows a rapid change in the temperaturewithlightheating.(SupplementaryFig.16) Temperaturedependence:AFEHZOisknowntoexhibittemperature-sensitivephasestability, often transitioning to FE-like states at elevated temperature. No temperature-dependent measurements (P–V,retention, or photoresponse) are provided. Such data wouldbe crucial to assessrobustnessandpracticaldeviceapplicability. Response: We sincerely thank the reviewer for this constructive comment regarding the temperature-dependent stability of the AFE Hf Zr O film. To address this concern, we 0.1 0.9 2 have performed additional systematic measurements at 353 K. PUND measurements (Fig. R3(a)) were conducted at this temperature, and the leakage contribution was subtracted to obtain the corrected P-V loop. The loop exhibits a slight reduction in polarization amplitude but retains robust switchable polarization characteristics. Furthermore, retention measurements (Fig. R9(b)), extrapolated via a log-linear fit, indicate that the film can maintain data for over ten years—well beyond the sensing margin required for nonvolatile memoryapplications.TheseresultsdemonstratethattheAFEHf Zr O filmpreserves both 0.1 0.9 2 substantial polarization and long-term retention at elevated temperatures, confirming its suitabilityforpracticaldeviceoperation.ThenewdataaresummarizedinSupplementaryFig. 12oftherevisedmanuscript. Fig. R9. (a) Corrected P-V characteristics of the PDA-processed GNS/Hf Zr O /W sample 0.1 0.9 2 obtained via PUND measurements at 295 K and 353 K. (b) Retention properties of the GNS/Hf Zr O /Wdevicemeasuredat353K.(SupplementaryFig.12) 0.1 0.9 2 Reliability and statistics: The endurance data (>10⁹ cycles) are impressive, but error bars or statistical variation across multiple devices are not reported. Including device-to-device distributionswouldmakethereliabilityclaimsmoreconvincing. Response: We sincerelythank the reviewer for this important suggestion regardingstatistical validationoftheendurance results.Toaddress this point,we have nowtestedthreeadditional devices under identical cycling conditions. All devices successfully endured over 10⁹ switching cycles without failure, and their P–V characteristics and endurance trends exhibit excellent consistency. The device-to-device variations are minimal, confirming the robust reliability of our fabrication process. These additional data have been included as Fig. R10 andreferencedintherevisedmanuscript(SupplementaryFig.11). Fig. R10. Additional endurance measurements on three more devices under the same conditions.(SupplementaryFig.12) Control experiments: The W-electrode control confirms the necessity of GNS, but additional controlsusingsemi-transparentelectrodes suchasITOor graphene wouldclarifywhether the response is uniquely enabled by GNS–HZO coupling or a more general optical absorption effect. Response: We sincerely thank the reviewer for this insightful suggestion. To further clarify the role of GNS, we fabricated devices with few-layer graphene as the top electrode (with Cr/Au contact pads to ensure reliable electrical connection) and performed identical measurements under the same conditions. The graphene-top-electrode device exhibited a similar P–V loop to that of the GNS–HZO device (Fig. R11 (a)), indicating comparable ferroelectric switching behavior. However, as presented in Fig. R11 (b), no discernible pyroelectric response was observed under identical laser excitation (475 nm, 2 mW/cm²), whichproduceda strong signal inthe GNS–HZO devices.This clearlycontrast demonstrates thattheGNS–HZOcouplingiscrucialfortheenhancedphoto-pyroelectriceffect. Fig. R11. (a) The P-V hysteresis loop and (b) photoresponse (475nm, 2mW/cm2) of the PDA-processedGraphene/Hf Zr O /Wdevice.(SupplementaryFig.15b,c) 0.1 0.9 2 [Methodologyandreproducibility] Thefabricationandmeasurementmethodsaredescribedinreasonabledetail.Theinclusionof supplementary figures on process flow, absorption spectra, and endurance characteristics is helpful.However,somemethodologicalclarificationsarestillneeded: Details of GNS transfer and interfacial cleanliness should be expanded, as interface quality criticallyaffectsferroelectricbehavior. Response: We sincerely thank the reviewer for this valuable suggestion. The dry transfer of GNS was performed on a dedicated two-dimensional material transfer station. Prior to the transfer, the target substrate was thoroughly cleaned via sequential ultrasonic cleaning in acetone, ethanol, and deionized water. Graphite nanosheets were mechanically exfoliated frombulkgraphiteusingpolymertapeandsubsequentlytransferredontoaPDMSstamp.The stampwascarefullyalignedwiththesubstrateunderopticalmicroscopy.Tominimizetrapped bubbles and ensure uniform contact, the PDMS was gradually pressed from one edge and slowly peeled from the same edge. After transfer, the sample underwent acetone immersion for 30 minutes to remove organic residues, followed by rinsing with ethanol and deionized water, and was finally dried under a nitrogen stream. The transferred interface was inspected under optical microscopy and confirmed to be free of noticeable bubbles. These procedures werespecificallyimplementedtoachieveaclean,residue-freevdWinterface,whichiscritical for maintaining robust ferroelectric switching in GNS-HZO devices. In our revised manuscript, we have added relevant content on the transfer of graphite nanosheets in the methodssection. Sharp–Garn pyroelectric coefficient measurements should include uncertainties and comparisonwithpriorreports. Response: We sincerely thank the reviewer for this important suggestion. In response, we have incorporated the measurement uncertainties into Fig. 4b. The pyroelectric coefficient obtainedunder-4Vpre-polingisapproximately-39.2±0.5μCm-2K-1,whichfallswithinthe commonly reported range for HfO2-based ferroelectric films (-30 to -70 μC m-2 K-1, Nano Energy 74 (2020) 104733). In contrast, under +4Vpre-poling, the coefficient is significantly reduced to -4.1 ± 0.4 μC m-2 K-1. This pronounced polarity dependence indicates that the effective pyroelectric response is closely linked to the pre-poling condition and the resulting polarizationstate,consistentwiththeferroelectricnatureofthefilm. [Overallassessment] The manuscript presents an innovative and promising device concept, and the experimental results are noteworthy. However, before publication in Nature Communications, additional quantitative analysis of screening effects, DOE/multiphysics modeling, and temperature dependence is required to fully support the conclusions. Addressing these points would not only validate the claims but also significantly enhance the impact and scientific rigor of the work. Response: We sincerely thank the Reviewer for their detailed and thoughtful review, as well asfortheverypositive feedbackonourwork.Wearegratefulfortheconstructivecomments, which have been extremely helpful in guiding us to further refine and strengthen our manuscript. In particular, we appreciate the Reviewer’s suggestion to include additional quantitative analysis of screening effects, DOE/multiphysics modeling, and temperature dependence.Wehavemadesubstantialrevisionstoaddressthesepoints,andwebelievethese improvements enhance both the scientific rigor and impact of the work. We have carefully addressed each comment raised and made every effort to incorporate the recommended additionsintherevisedmanuscript. ResponsetoReviewer#3’scomments: This paper describes a new non-volatile memory made of an antiferroelectric, Hf₀.₁Zr₀.₉O₂. Common antiferroelectric materials suffer from depolarization and have no distinct, stable polarizationstate.Thus,antiferroelectricmemorysuffersfromshortdataretentiontimeandis not yet practical. Furthermore, antiferroelectric memory typically reads data using an electric pulse, while the reading operation itself disturbs the data storage state and becomes destructive. Finally, antiferroelectric materials are sensitive to processing conditions, and commonprocessingtechnologymayfurtherdisruptthepolarizationstate.Thepaperdiscusses new strategies to overcome these challenges. Namely, these strategies include: (1) establishing energy barriers in two polarization states with a built-in electric field; (2) engineering the built-in field by matching top and bottom contacts with different work functions, namely graphite and tungsten contacts; (3) avoiding processing-induced defects by realizingacleanvanderWaalsinterfacebetweenthegraphitecontactandHf₀.₁Zr₀.₉O₂;and(4) utilizinganewlight-poweredopticalreadoutschemebycouplingthephoto-thermaleffectsof thegraphite contact withthe pyroelectricityof Hf₀.₁Zr₀.₉O₂ antiferroelectrics.These strategies resultinasandwichstructureofgraphite–Hf₀.₁Zr₀.₉O₂–tungstencapacitor. Withthesestrategies,thepaperdiscussesthepolarizationcharacteristicsandmeasuresseveral key metrics of non-volatile random-access memory based on Hf₀.₁Zr₀.₉O₂ antiferroelectrics. This sandwich structure of graphite–Hf₀.₁Zr₀.₉O₂–tungsten shows a clear bi-stable state of polarization and no polarization. Furthermore, these two states convert into each other via a ±4 V electrical pulse signal. In other words, these ±4 V pulses perform the writing operation of the memory. Over repeated electrical pulses, the device current shows strong decay. The paper reveals that such decay indicates polarization switching and data storage. After the writing operation, the paper further evaluates the capability and reliability of data retention. Over 10⁹ test cycles, the device maintains significant polarization and shows strong fatigue resistance. In the time domain, the paper projects a data retention time of over ten years, an industrystandardforpracticaldevices.Finally,the paper discussesoptical readout ofthe data state. The paper proposes that optical excitation heats the graphite electrode and the Hf₀.₁Zr₀.₉O₂ antiferroelectric, inducing a pyroelectric current. This pyroelectric current only appears with polarization; thus, the current serves as a sensitive fingerprint of the data state. Thepapershowsthepyroelectriccurrentisrobustacrossawiderange ofthevisiblespectrum and under optical power densities from 0.5 mW/cm² to 2 mW/cm². Promisingly, the pyroelectric current also appears under zero bias; therefore, the readout is solely powered by optical excitation. Taken together, the paper addresses the challenges with this novel device designandanopticallypowered,non-destructivereadoutmechanism. This paper presents new device designs. The device shows clear bi-stable states, electrically programmable memory effects, and optical accessibility. The devices also exhibit excellent dataretentiontimeandstrongrobustness;allthemeasurementsshowpromisingresults.Inthe meantime, I have several major comments on the rationale of the key idea anddevice design, as well as minor comments on device performance and measurement. I list all my comments below; I will happily evaluate this manuscript again once the authors discuss and address the concerns. Response: We sincerely thank the reviewer for the highly encouraging and thoughtful evaluation of our work. We are deeply grateful that you recognized the novelty of our device concept, the significance of the built-in field engineering strategy, and the robustness of the proposed optically powered, non-destructive readout mechanism. Your constructive feedback has been invaluable in helping us refine the physical interpretation and strengthen the overall scientific clarity of the manuscript. In response, we have carefully addressed all comments raised in your review and have made necessary revisions and additions throughout the manuscript to improve its rigor, consistency, and readability. We truly appreciate your time andexpertiseinprovidingsuchcomprehensiveandinsightfulfeedback. Majorcomments: 1.The major element of this proposeddevice design is work function engineering. The paper claimstousegraphitetoestablishabuilt-inpotentialandmodifytheenergylandscape.Inline 164, the paper claims the graphite nanosheet has a work function of 4.6–4.7 eV. The paper furthercitesworks ontheworkfunctionofcarbonnanotubes.However,(1)carbonnanotubes and graphite nanosheets do not necessarily have the same work function, and (2) 2D nanosheets often show interface-dependent work functions and exotic phenomena such as Fermi-level pinning. I suggest the authors better support this claim by measuring the work functionandbarrierheightoftheirdevice. Response: We sincerely thank the reviewer for this insightful comment. The reference we originally cited (Appl. Phys. Lett. 76, 4007–4009 (2000)) indeed reports measured work function values for both carbon nanotubes and graphite. The value of 4.6–4.7 eV used in our manuscript specificallyrefers to the graphite data in that study,not the carbonnanotube data. Weapologizeforanyambiguitythatmayhavearisenfromthearticle’stitle. In agreement withthe reviewer’s suggestion, we have alsoperformeddirectexperimental verification of the work function in our system. Using Molecular Vista Photoinduced Force Microscopy (Kelvin Probe Force Microscopy mode), we measured the contact potential difference between our graphite nanosheet and a gold reference electrode. The measured contact potential difference (Fig. R12) indicates that the work function of our graphite nanosheetisapproximately0.13eVlowerthanthatofgold.Consideringtheestablishedwork functionof gold inair (~4.67eV,Surface Science 481(2001) 172–184),the workfunctionof our graphite nanosheet is therefore ~4.68 eV. This value is in excellent agreement with the 4.6–4.7eVrangecitedforgraphiteinpriorstudies. To clarify this point, we have revised the main text to explicitly state that the cited value refers to graphite. In addition, we have included our KPFM measurement results in the SupplementaryFig.7toprovidedirectexperimentalsupportfortheworkfunctionofgraphite in our device. These results further strengthen the basis of our work function engineering argument. Fig. R12. Relative potential distribution diagram of gold and graphite nanosheet samples measuredbyKPFM.Scalebar,2 μm.(SupplementaryFig.7) 2. The paper also claims the graphite contact contributes to higher interfacial quality and higher nonzero remnant polarization Pᵣ (line 56, line 158). However, the paper hardly discusses any measurements on the interface. Since the interface consists of anALD-grown thin film and a 20-nm-thick graphite layer, the exact interface quality is complex. Consider thefollowingissues.(1)Thegraphiteisverythick.Thickbulkgraphiteislikelytohavesharp steps and form several-nm-wide air gaps when stacked on the antiferroelectric. In this sense, van der Waals interaction does not adequately describe the interface. (2) Even in regions without air gaps, how clean is the interface? The dry transfer process often results in many defects such as polymer contamination, trapped air bubbles, and gaps. I feel it is necessary to include these metrics when reporting the interface quality and quantifying the van der Waals interface.Currently,theinterfacialqualityremainsunclear. Response: We sincerely thank the reviewer for raising these important points regarding the interfacial quality between the graphite and the antiferroelectric thin film. We acknowledge that the dry transfer of thick graphite can pose challenges due to potential air gaps. To mitigate such issues, we carefully optimized the transfer process: the PDMS stamp was gradually pressed from one edge while slowly peeling from the same side, promoting progressive contact and allowing trapped air to escape. Optical microscopy inspection during and after transfer confirmed that the graphite flakes adhered uniformly to the substrate withoutvisiblebubblesorgapsintheregionsselectedfordevicefabrication. To directly address the impact on electrical properties, we performed a controlled experiment: devices with intentionally introduced bubbles in the graphite layer exhibited reducedremnant polarization (Pᵣ) comparedto devices with continuous graphite contact (Fig. R13). This comparison confirms that our optimized transfer achieves sufficient interfacial contact, and that the enhanced performance in our devices is indeed linked to the improved interfacequality. Furthermore, to quantitatively assess surface cleanliness, we performed Raman spectroscopy (HORIBA HR Evolution) on the transferred graphite electrodes. The spectra (Fig. R14) show only the prominent G and 2D peaks characteristic of pristine graphite, with no additional peaks indicative of contamination. This demonstrates that our dry transfer process—usingaPDMSstampwithoutintermediatepolymers—successfullyavoidschemical residues.Thisconclusionis supportedbyestablishedliterature[ACSNano 2011, 5(3),2362 –2368]whichcorrelatesacleanRamanspectrumwithacontaminant-freegraphitesurface. Fig.R13.Area-dependentpolarizationbehaviorinGNS/Hf Zr O /Wdevicewithbubbles. 0.1 0.9 2 Fig. R14. Representative Raman spectrum of a transferred graphite electrode on the antiferroelectric film. (Supplementary Fig. 3) The spectrum exhibits only the characteristic G and 2D peaks of graphite, with no observable peaks from polymer residues or other contaminants. 3. The paper reports two methods to induce a built-in electrical field: post-deposition annealing and asymmetric contacts. In particular, in Figure 2 and Supporting Figure 4, the devices with post-deposition annealing alone already show decent remnant polarization Pᵣ. The paper also mentions that annealing per se is more effective than work function engineering (line 171). How much does the graphite contact contribute to boosting the remnantpolarizationPᵣ? Response: We sincerely thank the reviewer for this insightful comment and for emphasizing the effectiveness of the post-deposition annealing (PDA) process. As you astutely noted, our PDA method streamlines the fabrication by eliminating the multiple steps (post-metallization annealing + Standard Cleaning 1 removal) otherwise required in the work function engineering approach, while still achieving a similar—and in our case, superior—built-in field. At the same time, the choice of top electrode remains important. Devices with graphite top electrodes exhibit a 2Pᵣ of ~30 μC/cm², which is notably higher than devices with symmetric Ni electrodes (2Pᵣ ~22 μC/cm²), Cr electrodes (2Pᵣ ~14 μC/cm²), or W electrodes (2Pᵣ ~9 μC/cm²). The use of an asymmetric graphite contact further boosts the remnant polarization by ~36% compared to the best-performing symmetric metal contact (Ni). This demonstrates that the graphite contact plays a significant complementary role in enhancing theoverallpolarization. Minorcomments 1. In Figure 4(c), the paper discusses the time response of the pyroelectric current signal. Figure 4(c)shows a typical readout process lastingatleast 0.1second.Whyis this process so slow?Whichstepistherate-limitingstep?Iwillalsowelcome ashortdiscussiononpotential planstomakethereadoutfasterforpracticaldevices. Response: We sincerely thank the reviewer for the careful reading of our manuscript and for raising this important question regarding the readout time in Fig. 4(c). The pyroelectric current pulses appear only at the light-on and light-off transitions because our readout is proportional todT/dt.The ~0.1 s timescale observed inFig.4(c) isprimarily governedby the thermal time constant [Incropera & DeWitt, Fundamentals of Heat and Mass Transfer,Wiley, 2013; Rev. Sci. Instrum. 62, 797-804 (1991)] of the stack—namely, heat diffusion and relaxation between the absorbing graphite layer, the ferroelectric HZO film, and the underlying metal/substrate. A secondary limitation may arise from the front-end electronics (transimpedance amplifier feedback and parasitic capacitance), which reduce the effective measurementbandwidthwhenlargefeedbackresistancesareusedforhighsensitivity. To verify the origin of the time constant, we conducted an additional experiment using stronger illumination and a higher-bandwidth readout. The optical excitation frequency was increased while maintaining the same device structure and electrical bias. As shown in Fig. R14, the transient current pulses followed the faster optical modulation without distortion, and the response time was markedly shortened to ~17ms (still limited by the sampling speed oftheelectricalinstrument,Keithley4200),confirmingthatfasteropticalreadoutisfeasible. For practical implementations, the readout speed can be further enhanced by engineering both the thermal path and the electronic front-end—for example, by reducing the absorber and active-layer thickness, optimizing electrode thermal mass, employing a faster thermal sink, or replacing the current preamplifier with a higher-bandwidth design. These strategies allowa tunable trade-offbetweenresponsivity andspeed,dependingonthe target application (e.g.,high-speedopticalsensingversusmaximumsensitivity). Fig. R15. Faster optical readout verified by transient current response under higher illuminationandbandwidthconditions.(SupplementaryFig.14) 2. In addition to the graphite–Hf₀.₁Zr₀.₉O₂–tungsten stack, the final device also has a 5 nm thick chromium layer on graphite.A5 nm metal deposition on 2D nanosheets often forms islands instead of a continuous thin film, and the paper would benefit from a quick clarification. Furthermore, assuming a continuous thin film, how does this 5 nm thick chromiumlayeraffectlightabsorptionefficiency? Response:Wesincerelythankthereviewerfor thisinsightful comment regardingthe5 nm Cr layer.As noted, such a thin metal deposition can indeed form a discontinuous film. In ourwork,theCrlayerwasdepositedsolelyasaprotectivecappinglayertopreventdamage totheunderlyinggraphiteduringFocusedIonBeam(FIB)millingforcross-sectionalTEM analysis. It is therefore used only for sample preparation and characterization, and is not partofthefunctionaldevicestackemployedinouroptoelectronicmeasurements. As a result, this Cr layer does not influence the device operation, including light absorption or the pyroelectric response, which are governed entirely by the GNS/Hf Zr O /W structure. To avoid any confusion, we have revised the manuscript to 0.1 0.9 2 explicitly clarify the role of the Cr layer and confirm that it does not affect the device’s photo-pyroelectricfunctionality. 3. The paper uses excessive abbreviations, such as GNS, PMA, PDA, TE, BE, etc. These abbreviations significantly slow down and hinder understanding of the manuscript and are unnecessary. Please refrain from and remove non-standard abbreviations as much as possible. Response: We sincerely thank the reviewer for this helpful suggestion. We agree that excessive abbreviations can reduce readability and have thoroughly revisedthe manuscript to minimize their use. Specifically, the full terms post-metallization annealing and bottom electrodearenowwrittenoutinsteadof“PMA”and“BE,”respectively. We have retained only two abbreviations—“GNS” (graphene nanosheets) and “PDA” (post-deposition annealing)—as they appear very frequently throughout the text and are well-established in related literature. This limited use helps maintain conciseness without sacrificingclarity. Theterm“TE”(topelectrode)isnowusedonlyinfigurelegends,wherespaceconstraints make abbreviation necessary. We believe these revisions substantially improve the manuscript’sreadabilityandconsistency. Responsetoreviewers Reviewer#1: The authors have adequately addressed all reviewer comments, and the manuscript is recommendedforpublication. Response: We sincerely thank the reviewer for the thorough review and helpful suggestions throughout the revision process. We appreciate the positive recommendation and are pleased thatthemanuscriptisnowsuitableforpublication. Reviewer#2: The authors have thoroughly addressed all of the concerns raised in the initial review. The revised manuscript shows substantial improvement in clarity, scientific rigor, and completenessoftheexperimentalandanalyticalevidence. Specifically,theauthorshave: Provided a quantitative and well-supported discussion on electronic screening, including screeninglengths,depolarizationfieldmodeling,andupdatedbanddiagrams. These additions significantly strengthen the mechanistic understanding of the GNS–HZO interface. Performed comprehensive multiphysics simulations (optical–thermal–electrical) using COMSOL, which convincingly validate that the observed transient signals originate from genuinepyroelectricprocessesratherthanthermalleakage. ThenewSupplementaryfiguresmakethisinterpretationveryclear. Added temperature-dependent P–V and retention measurements, demonstrating the stability oftheAFEHZOlayeratelevatedtemperature(353K). Thisstronglysupportsthepracticalrobustnessofthedeviceconcept. Included device-to-device statistics for endurance, showing excellent reproducibility and confirmingthereliabilityofthefabricationprocess. Performedadditionalcontrolexperimentsusinggrapheneelectrodes. The comparison further highlights that the enhanced photo-pyroelectric response is unique to theGNS–HZOcouplingmechanism. Expanded methodological details, particularly regarding GNS transfer and pyroelectric coefficientextraction,includinguncertaintyanalysisandcomparisontoliteraturevalues. Theseadditionsgreatlyimprovereproducibility. Overall, the authors have gone above and beyond in responding to each comment with new experiments, simulations, and clearer explanations. The manuscript is now significantly strengthened and presents a compelling, original, and well-validated study that will be of broadinteresttothecommunity. I believe the manuscript is now suitable for publication in Nature Communications without furtherrevision. Response: We sincerely thank the reviewer for the careful review and encouraging feedback. We greatly appreciate the acknowledgment of the additional experiments, simulations, and explanations,andarepleasedthatthemanuscriptisnowconsideredsuitableforpublication. Reviewer#3: In the revision, the authors have satisfactorily addressed all my questions. I therefore recommendthatthisworkbepublishedasis. Response:We sincerely thank Reviewer for the careful review and positive feedback. We are gratefulfortherecommendationtopublishourworkinNatureCommunications."}, {"round": 2, "reviewer_comments": {"reviewer_1": "The authors have adequately addressed all reviewer comments, and the manuscript is recommended for publication.", "reviewer_2": "The authors have thoroughly addressed all of the concerns raised in the initial review. The revised manuscript shows substantial improvement in clarity, scientific rigor, and completeness of the experimental and analytical evidence. Specifically, the authors have: Provided a quantitative and well-supported discussion on electronic screening, including screening lengths, depolarization field modeling, and updated band diagrams. These additions significantly strengthen the mechanistic understanding of the GNS–HZO interface. Performed comprehensive multiphysics simulations (optical–thermal–electrical) using COMSOL, which convincingly validate that the observed transient signals originate from genuine pyroelectric processes rather than thermal leakage. The new Supplementary figures make this interpretation very clear. Added temperature-dependent P–V and retention measurements, demonstrating the stability of the AFE HZO layer at elevated temperature (353 K). This strongly supports the practical robustness of the device concept. Included device-to-device statistics for endurance, showing excellent reproducibility and confirming the reliability of the fabrication process. Performed additional control experiments using graphene electrodes. The comparison further highlights that the enhanced photo-pyroelectric response is unique to the GNS–HZO coupling mechanism. Expanded methodological details, particularly regarding GNS transfer and pyroelectric coefficient extraction, including uncertainty analysis and comparison to literature values. These additions greatly improve reproducibility. Overall, the authors have gone above and beyond in responding to each comment with new experiments, simulations, and clearer explanations. The manuscript is now significantly strengthened and presents a compelling, original, and well-validated study that will be of broad interest to the community. I believe the manuscript is now suitable for publication in Nature Communications without further revision.", "reviewer_3": "In the revision, the authors have satisfactorily addressed all my questions. I therefore recommend that this work be published as is."}, "author_response": ""}]

Decision letter