Ferroelectric Pb Zr Research Articles

A Time-Domain Perspective on the Structural and Electronic Response in Epitaxial Ferroelectric Thin Films on Silicon.

This operando study of epitaxial ferroelectric Pb(Zr0.48Ti0.52)O3 capacitors on silicon substrates studies their structural response via synchrotron-based time-resolved X-ray diffraction during hysteresis-loop measurements in the 2-200 kHz range. At high frequencies, the polarization hysteresis loop is rounded and the classical butterfly-like strain hysteresis acquires a flat dumbbell shape. We explain these observations from a time-domain perspective: The polarization and structural motion within the unit cell are coupled to the strain by the piezoelectric effect and limited by domain wall velocity. The solution of this coupled oscillator system is derived experimentally from the simultaneously measured electronic and structural data. The driving stress σFE(t) is calculated as the product of the measured voltage U(t) and polarization P(t). Unlike the electrical variables, σFE(t) and η(t) of the ferroelectric oscillate at twice the frequency of the applied electrical field. We model the measured frequency-dependent phase shift between η(t) and σFE(t).

Nonvolatile Modulation of Bi2O2Se/Pb(Zr,Ti)O3 Heteroepitaxy.

The pursuit of high-performance electronic devices has driven the research focus toward 2D semiconductors with high electron mobility and suitable band gaps. Previous studies have demonstrated that quasi-2D Bi2O2Se (BOSe) has remarkable physical properties and is a promising candidate for further exploration. Building upon this foundation, the present work introduces a novel concept for achieving nonvolatile and reversible control of BOSe's electronic properties. The approach involves the epitaxial integration of a ferroelectric PbZr0.2Ti0.8O3 (PZT) layer to modify BOSe's band alignment. Within the BOSe/PZT heteroepitaxy, through two opposite ferroelectric polarization states of the PZT layer, we can tune the Fermi level in the BOSe layer. Consequently, this controlled modulation of the electronic structure provides a pathway to manipulate the electrical properties of the BOSe layer and the corresponding devices.

Fault-tolerant structures against breakdown in heterogeneous ferroelectric PbZr0.52Ti0.48O3 thin films based on adaptive self-repairing effects

The design of fault-tolerant structures against the breakdown of heterogeneous ferroelectric films is essential to enhance the breakdown strength. Based on the self-repairing theory, heterogeneous ferroelectric PbZr0.52Ti0.48O3 (PZT) film capacitors with a fault-tolerant structures against breakdown were synthesized by utilizing dielectric/electrolytic dual characteristics of the amorphous aluminum oxide film (AmAO). The PZT/AmAO composite films with Au top electrodes exhibited significant weak breakdown at low voltages, whereas the breakdown in the composite films with Al top electrodes have been repaired and no longer occurred. Compared to PZT(100 nm)/AmAO(120 nm) composite films with Au top electrodes, breakdown strength of PZT(100 nm)/AmAO(120 nm) composite films with Al top electrodes improves from 278 MV/m to 477 MV/m, energy storage density increased from 14.3 J/cm3 to 22.5 J/cm3, since the heterogeneous interface and structural defects have been repaired by adaptive anodizing of Al electrode under high electric field. Cross-sectional SEM images have confirmed the formation of fresh aluminium oxide films (AAO) at the interfaces of AmAO/Al and PZT/AmAO during the application of an electric field. Defects have been effectively repaired, resulting in an increase in breakdown strength. This study establishes a theoretical and technical foundation for the design of fault-tolerant structures against breakdown in heterogeneous ferroelectric films.

Record high room temperature resistance switching in ferroelectric-gated Mott transistors unlocked by interfacial charge engineering

The superior size and power scaling potential of ferroelectric-gated Mott transistors makes them promising building blocks for developing energy-efficient memory and logic applications in the post-Moore’s Law era. The close to metallic carrier density in the Mott channel, however, imposes the bottleneck for achieving substantial field effect modulation via a solid-state gate. Previous studies have focused on optimizing the thickness, charge mobility, and carrier density of single-layer correlated channels, which have only led to moderate resistance switching at room temperature. Here, we report a record high nonvolatile resistance switching ratio of 38,440% at 300 K in a prototype Mott transistor consisting of a ferroelectric PbZr0.2Ti0.8O3 gate and an RNiO3 (R: rare earth)/La0.67Sr0.33MnO3 composite channel. The ultrathin La0.67Sr0.33MnO3 buffer layer not only tailors the carrier density profile in RNiO3 through interfacial charge transfer, as corroborated by first-principles calculations, but also provides an extended screening layer that reduces the depolarization effect in the ferroelectric gate. Our study points to an effective material strategy for the functional design of complex oxide heterointerfaces that harnesses the competing roles of charge in field effect screening and ferroelectric depolarization effects.

Giant Energy Density via Mechanically Tailored Relaxor Ferroelectric Behavior of Pzt Thick Film.

Relaxor ferroelectrics (RFEs) are being actively investigated for energy storage applications due to their large electric-field-induced polarization with slim hysteresis and fast energy charging-discharging capability. Here, w e report a novel nanograin engineering approach based upon high kinetic energy deposition for mechanically inducing the RFE behavior in a normal ferroelectric Pb(Zr0.52 Ti0.48 )O3 (PZT), which results in simultaneous enhancement in the dielectric breakdown strength (EDBS ) and polarization. Mechanically transformed relaxor thick films with 4μm thickness exhibited an exceptional EDBS of 540 MV/m and reduced hysteresis with large unsaturated polarization (103.6 μC/cm2 ), resulting in a record high energy storage density of 124.1 J/cm3 and a power density of 64.5 MW/cm3 . This fundamental advancement is correlated with the generalized nanostructure design that comprises of nanocrystalline phases embedded within the amorphous matrix. Microstructure-tailored ferroelectric behavior overcomes the limitations imposed by traditional compositional design methods and provides a feasible pathway for realization of high-performance energy storage materials. This article is protected by copyright. All rights reserved.

Interface-Tuning of Ferroelectricity and Quadruple-Well State in CuInP2S6 via Ferroelectric Oxide.

Ferroelectric van der Waals CuInP2S6 possesses intriguing quadruple-well states and negative piezoelectricity. Its technological implementation has been impeded by the relatively low Curie temperature (bulk TC ∼ 42 °C) and the lack of precise domain control. Here we show that CuInP2S6 can be immune to the finite size effect and exhibits enhanced ferroelectricity, piezoelectricity, and polar alignment in the ultrathin limit when it is interfaced with ferroelectric oxide PbZr0.2Ti0.8O3 films. Piezoresponse force microscopy studies reveal that the polar domains in thin CuInP2S6 fully conform to those of the underlying PbZr0.2Ti0.8O3, where the piezoelectric coefficient changes sign and increases sharply with reducing thickness. High temperature in situ domain imaging points to a significantly enhanced TC of >200 °C for 13 nm CuInP2S6 on PbZr0.2Ti0.8O3. Density functional theory modeling and Monte Carlo simulations show that the enhanced polar alignment and TC can be attributed to interface-mediated structure distortion in CuInP2S6. Our study provides an effective material strategy to engineer the polar properties of CuInP2S6 for flexible nanoelectronic, optoelectronic, and mechanical applications.

Enhanced synaptic weight in ferroelectric PbZr0.52Ti0.48O3 thin film by inserting semiconductor Sr2IrO4 layer

Ferroelectric memristors based on metal/ferroelectric/semiconductor structure are suitable for the simulation of non-volatile synaptic weight due to the high on/off switching ratio, low energy consumption, high precision and fast working speed. Especially, the characteristics of the semiconductor electrode are closely related to the synaptic performance of the device. Here, ferroelectric memristors (PbZr0.52Ti0.48O3/Nb:SrTiO3 and PbZr0.52Ti0.48O3/Sr2IrO4) with different semiconductor electrodes were fabricated by introducing Sr2IrO4 (SIO) thin film. Various plasticity have been successfully simulated under different electrical impulses, such as inhibitory postsynaptic current (IPSC), paired pulse depression (PPD), spike rate dependent plasticity (SRDP) and spike time dependent plasticity (STDP) in the two devices. Moreover, the absolute values of synaptic weight and the relaxation time of PbZr0.52Ti0.48O3 (PZT)/SIO have been significantly improved. This may be attributed to the fact that the small work function of SIO increases the variation of the interface barrier at the device. And the artificial synaptic device based on PZT/SIO is used to achieve the application of Morse code. This study plays an important role in achieving efficient storage and computation for neuromorphic computing.

Enhanced synaptic performances in SrIrO3 thin films by a ferroelectric layer

SrIrO3 (SIO) with a perovskite structure exhibits broad application prospects in electronic synapses due to its high carrier mobility, scalability, and compatibility with silicon technology. On the other hand, ferroelectric polarization can efficiently and directionally regulate the movement of carriers, which provides the possibility to improve the synaptic properties of such materials. In this study, electronic synapses based on the SIO epitaxial film with introducing a ferroelectric PbZr0.2Ti0.8O3 (PZT) layer, multiple important synaptic plasticity functions including paired-pulse depression, spike-rate-dependent plasticity, spike-time-dependent plasticity, and abnormal Bienenstock–Cooper–Munro learning rule have been simulated by electrical stimulation. Furthermore, the PZT/SIO/Nb:SrTiO3 (NSTO) device exhibits larger synaptic weight and dynamic range of conductance and requires less training pulses compared to the SIO/NSTO device, which may be attributed to the enhanced modulation of the variation in the SIO/NSTO interface barrier by the polarization field. This research makes a great contribution to the efficient and fast information transmission of neuromorphic computing.

Implementation of threshold- and memory-switching memristors based on electrochemical metallization in an identical ferroelectric electrolyte

The use of an identical electrolyte in electrochemical metallization (ECM)-based neuron and synaptic devices has not yet been achieved due to their different resistive-switching characteristics. Herein, we describe ECM devices comprising the same ferroelectric PbZr0.52Ti0.48O3 (PZT) electrolyte, which can sustain both neuron and synaptic behavior depending on the identity of the active electrode. The Ag/PZT/La0.8Sr0.2MnO3 (LSMO) threshold switching memristor shows abrupt and volatile resistive switching characteristics, which lead to neuron devices with stochastic integration-and-fire behavior, auto-recovery, and rapid operation. In contrast, the Ni/PZT/LSMO memory switching memristor exhibits gradual, non-volatile resistive switching behavior, which leads to synaptic devices with a high on/off ratio, low on-state current, low variability, and spike-timing-dependent plasticity (STDP). The divergent behavior of the ECM devices is attributed to greater control of cation migration through the ultrathin ferroelectric PZT. Thus, ECM devices with an identical ferroelectric electrolyte offer promise as essential building blocks in the construction of high-performance neuromorphic computing systems.

Synthesis of freestanding perovskite oxide thin films by using brownmillerite SrCoO2.5 as a sacrificial layer

Freestanding perovskite thin films display many unprecedented properties and exhibit the potential to be easily integrated on other non-oxide substrates or layers. In this work, we demonstrated a pathway to synthesis freestanding perovskite oxide thin films by using brownmillerite SrCoO2.5 as a sacrificial layer. Four representative freestanding perovskite oxide films, e.g., ferromagnetic SrRuO3, La0.7Sr0.3MnO3, dielectric SrTiO3, and ferroelectric Pb(Zr0.2Ti0.8)O3, were produced by etching SrCoO2.5 in Fe(NO3)3 weak acidic solution at room temperature. A 80 nm SrRuO3, which served as an H+ conduction channel, was deposited as a bottom layer of SrCoO2.5 to trigger a quick dissolution for the exfoliation of SrTiO3 and Pb(Zr0.2Ti0.8)O3 poor H+ conductor. Their crystal structure and physical properties were well retained in transferred films. Our work demonstrated the wide applicability of SrCoO2.5 as a sacrificial layer on the synthesis of freestanding perovskite oxide thin films.

Direct magnetoelectric and magnetodielectric studies of electrospun Ba2Ni2Fe12O22–Pb(Zr0.52Ti0.48)O3 core–shell nanofibers

This article reports the synthesis of barium nickel hexaferrite-lead zirconium titanate (Ba2Ni2Fe12O22-Pb(Zr0.52Ti0.48)O3) core-shell nanofibers through sol-gel electrospinning method. Direct magnetoelectric and magnetodielectric coupling studies were performed on the synthesized electrospun core-shell nanofibers. The structure, functional, morphological, magnetic, dielectric, leakage current, and ferroelectric properties were also analyzed. X-ray diffraction studies revealed the hexagonal crystal structure of the core and the tetragonal structure of the shell. The Fourier transform infrared spectroscopy analysis showed the fundamental functional groups present in the nanofibers. Scanning electron microscopy studies showed that the diameter of the nanofibers was 404 nm, and elemental analysis by energy-dispersive X-ray spectroscopy showed the stoichiometric formation of Ba2Ni2Fe12O22 and Pb(Zr0.52Ti0.48)O3 in the composite. Microstructure studies using a transmission electron microscope revealed the formation of core-shell nanofibers with a clear interface between the magnetic Ba2Ni2Fe12O22 (BNFO) core and the ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) shell. Selected-area electron diffraction analysis showed the Ba2Ni2Fe12O22 and Pb(Zr0.52Ti0.48)O3 phases to be highly crystalline. At room temperature, the synthesized nanofibers exhibited well-defined ferroelectric and magnetic hysteresis loops. Dielectric and leakage current studies were performed. Direct magnetoelectric and magnetodielectric studies were also performed to study the cross-coupling between the ferroic orders of the nanofiber. Moreover, using Landau’s energy expression, the type of magnetoelectric coupling was proved to be biquadratic. The enhanced magnetoelectric behavior of the Ba2Ni2Fe12O22–Pb(Zr0.52Ti0.48)O3 core–shell nanofiber confirms that the nanofiber is a potential candidate for high-performing magnetic field sensors, magnetically tuned capacitors, multimedia transducers, and spintronic devices.

Large Thermal Conductivity Switching in Ferroelectrics by Electric Field-Triggered Crystal Symmetry Engineering

A convenient, reversible, fast, and wide-range switching of thermal conductivity is desired for efficient heat energy management. However, traditional methods, such as temperature-induced phase transition and chemical doping, have many limitations, e.g., the lack of continuous tunability over a wide temperature range and low switching speed. In this work, a strategy of electric field-driven crystal symmetry engineering to efficiently modulate thermal conductivity is reported with first-principles calculations. By simply changing the direction of an external electric field loaded in ferroelectric PbZr0.5Ti0.5O3, near the morphotropic phase boundary composition, we obtain the largest switching of thermal conductivity for ferroelectric materials at room temperature based on the dual-phonon theory, i.e., normal and diffuson-like phonons, with three different criteria. The calculation results indicate that with decreasing crystal symmetry, the degeneracy of phonon modes reduces and the avoid-crossing behavior of phonon branches enhances, leading to the increase of diffuson-like phonons and weighted phonon-phonon scattering phase space. A thermal switch prototype based on PbZr0.5Ti0.5O3 is further shown that can protect the Li-ion battery by modulating its temperature up to 17.5 °C. Our studies would pave the way for designing next-generation thermal switch with high speed, a wide temperature range, and a large switching ratio.

Flexible ferroelectric Pb(Zr0.53Ti0.47)O3 epitaxial films with large radiation and high-temperature tolerance

Radiation and temperature hardness are important for electronic devices operating in harsh environments such as modern medical equipment, outer space, and nuclear energy industries. In this work, we report radiation and temperature-hardened flexible ferroelectric Pb(Zr0.53Ti0.47)O3 epitaxial films that were grown on flexible inorganic mica substrates via van der Waals heteroepitaxy and can be further used for building high-performance electronic devices. We systematically investigated the effect of 60Co-gamma radiation and temperature on the ferroelectric properties of Pb(Zr0.53Ti0.47)O3 films and their flexibility as well. Pb(Zr0.53Ti0.47)O3 films exhibit a radiation and temperature tolerance of up to 20 Mrad and 175 °C, respectively. In particular, the 20 Mrad-irradiated Pb(Zr0.53Ti0.47)O3 film has an excellent retention even after 105 s with extrapolate retention time longer than 10 years and polarization fatigue up to 1010 cycles as well as moderate flexibility and bending stability after bending 105 cycles. Furthermore, we identified that the degradation of macroscopic ferroelectric properties of irradiated Pb(Zr0.53Ti0.47)O3 films originates from the ferroelectric domain pinning effect induced by the ionization effect. Our work demonstrates that flexible ferroelectric Pb(Zr0.53Ti0.47)O3 films are promising for developing novel flexible electronic devices for applications in harsh environments.

Wireless Multiferroic Memristor with Coupled Giant Impedance and Artificial Synapse Application

AbstractInternet of things (IoT) becomes part of everyday life across the globe, whose nodes are able to sense, store, and transmit information wirelessly. However, the IoT nodes based on von Neumann architectures realize the memory, computing and communication functions with physical separated devices, which result in severe power consumption and computation latency. In this study, a wireless multiferroic memristor consisting of Metglas/Pb(Zr0.3Ti0.7)O3‐1 mol% Mn/Metglas laminate is proposed, which integrates the storage, processing, and wireless communication of information in a single device at the first time. First, a power efficient impedance modulation mechanism is explored for the multiferroic memristor, which couples electric field modulated giant magnetoimpedance (GMI) of magnetostrictive Metglas with varied impedance of ferroelectric Pb(Zr0.3Ti0.7)O3‐1 mol% Mn due to the gradual polarization switching. Meanwhile a pair of multiferroic memristors are used to transmit and receive stored information wirelessly, which facilitate the application of memristor in the IoT. Furthermore, the experimental study demonstrates that the memristor can mimic the synaptic plasticity, such as long‐term potentiation, depression, and spiking‐timing‐dependent plasticity, and it also reveals the capability of pattern learning with a memristor network. This work paves a way toward the IoT nodes integrating both brain inspired computing and wireless communication functions.

Effect of Cu ion implantation on charge transport of the PbZr0.52Ti0.48O3/FAPbI3 interface

The ferroelectric materials provide a way to improve and tune the photovoltaic performance of perovskite solar cells (PSCs), however, the improvement of device efficiency is limited by the interfacial electron transport. Here, we used ferroelectric PbZr0.52Ti0.48O3 (PZT) as the electron transport layer (ETL) in PSCs and investigated the effect of Cu ion implantation modified PZT on interfacial charge transport. The experimental results indicate that Cu ion implantation can improve the interface charge transport performance of the device. Under the results of SRIM simulation and density functional theory (DFT) calculation analysis, ion implantation leads to the generation of band-edge states in PZT. The interfacial electronic structure affected by the Cu ion implantation enhances the extract of photogenerated carriers and promotes charge transfer at the interface, besides reducing the recombination probability of carriers in the interface, which are good explanations of experimental phenomena.

Ferroelectric photosensor network: an advanced hardware solution to real-time machine vision

Nowadays the development of machine vision is oriented toward real-time applications such as autonomous driving. This demands a hardware solution with low latency, high energy efficiency, and good reliability. Here, we demonstrate a robust and self-powered in-sensor computing paradigm with a ferroelectric photosensor network (FE-PS-NET). The FE-PS-NET, constituted by ferroelectric photosensors (FE-PSs) with tunable photoresponsivities, is capable of simultaneously capturing and processing images. In each FE-PS, self-powered photovoltaic responses, modulated by remanent polarization of an epitaxial ferroelectric Pb(Zr0.2Ti0.8)O3 layer, show not only multiple nonvolatile levels but also sign reversibility, enabling the representation of a signed weight in a single device and hence reducing the hardware overhead for network construction. With multiple FE-PSs wired together, the FE-PS-NET acts on its own as an artificial neural network. In situ multiply-accumulate operation between an input image and a stored photoresponsivity matrix is demonstrated in the FE-PS-NET. Moreover, the FE-PS-NET is faultlessly competent for real-time image processing functionalities, including binary classification between ‘X’ and ‘T’ patterns with 100% accuracy and edge detection for an arrow sign with an F-Measure of 1 (under 365 nm ultraviolet light). This study highlights the great potential of ferroelectric photovoltaics as the hardware basis of real-time machine vision.

Realization of self-powered bidirectional photoresponse in the ultraviolet/visible wavelength region in ferroelectric heterojunctions

Broadband and wavelength selective photodetection are of great importance for photodetectors in practical applications, while these two features are generally in conflict with each other in conventional semiconductor heterojunctions. In the current work, CH3NH3PbBr3/PbZr0.52Ti0.48O3 ferroelectric heterojunction photodetectors have been demonstrated to obtain a self-powered bidirectional photoresponse, which realized a broadband and wavelength selective photodetection in the ultraviolet (UV)/visible wavelength region. By a combination of bulk photovoltaic effects of ferroelectric PbZr0.52Ti0.48O3 and built-in electric field at the CH3NH3PbBr3/PbZr0.52Ti0.48O3 heterojunction interface, the photodetectors exhibited a positive sensitivity in the UV spectral range and a negative sensitivity in the visible spectral range. Specifically, the sensitivities were +0.22 mA/W at 340 nm and −0.032 mA/W at 530 nm, both at the bias voltage of 0 V. Notably, the photoresponse polarity in the UV spectral range can be further reversed through electrically polarizing the ferroelectric PbZr0.52Ti0.48O3. The results provided in this work highlight the superiorities of ferroelectric heterojunction photodetectors and open a window for the fabrication of broadband and wavelength selective photodetectors.

Retracted] Application and Equipment of Preparation Technology of Ferroelectric Thin Film Materials in Sports Industry

With the rapid development of the integrated circuit industry, ferroelectric thin film materials and technologies have become increasingly important. Ferroelectric materials have been widely used in aerospace, information storage, artificial intelligence, microelectromechanical, wearable devices, and other fields. Traditional sports is an important carrier of traditional culture. It contains the sports cultural resources created and precipitated by the Chinese nation for thousands of years, and all sectors of society are also paying great attention to this. Under the background of the market economy system and the major premise of the vigorous development of the cultural industry and sports industry, industrialization is obviously the inevitable choice for traditional sports to break through the difficulties and seek development, and it will also promote the further inheritance and promotion of traditional sports. The complex combination causes its performance to decrease or even fail. Therefore, it cannot cause foresee losses and disasters. It has important application value and significance to master the performance changes and mechanisms of ferrous film materials under different adding environments. This paper takes ferroelectric Pb (Zr0.52Ti0.48)O3(PZT)Bi3.15Nd0.85Ti3O12(BNT) as the research object, proposes the preparation of sol coating for thin film materials, and studies the preparation parameters PZT of the sol electric ferroelectric method. Electrical method and BNT electrical film properties affect iron and physical experiments on the properties of iron. The influence of the best sol‐iron coating method on the electrical properties of PZT and BNT films is the ferroelectric properties of the 700°C layer of high‐temperature gas, 10‐layer PZT films, and 8‐layer BNT films. The elasticity and elastic moduli of PZT and BNT films are 66.8 MPa and 99.6 MPa and 159.3 GPa and 189GPa, respectively; the elastic coefficients of PZT and BNT films are15.4 × 1010 N/m2 and18.4 × 1010 N/m2, and their elastic coefficients|e31|decrease with accompanying increase in swallowing. And with the disease of reading and writing field strength, as the speed becomes faster and slower, the carriers have more time to move to the brain wall, so the intensity is also intuitive. It has strong practicability and feasibility to popularize the material and manufacture the equipment of the current sports equipment club.

High-performance self-powered visible-blind ultraviolet photodetection achieved by ferroelectric PbZr0.52Ti0.48O3 thin films

Self-powered visible-blind ultraviolet (UV) photodetection has been generally achieved based on the built-in electric field formed within the complicated devices such as pn or Schottky junctions, which involves a complicated device fabrication process. In contrast, employing the ferroelectric materials featured with unique bulk photovoltaic effect as absorbers will simplify the device structure and the subsequent device fabrication process without losing the performance of self-powered photodetection. In the current work, the fabrication of high-performance self-powered visible-blind UV photodetectors based on ferroelectric PbZr0.52Ti0.48O3 (PZT) thin films has been reported. The results showed that the spin-coated PZT thin films exhibited superior ferroelectric properties. On this basis, an efficient, stable, and repeatable self-powered UV photodetection has been achieved in the Au/PZT/FTO (fluorine-doped tin oxide) structured devices with the responsivity and detectivity as high as 0.092 A/W and 1.2 × 1012 Jones, respectively. More interestingly, the self-powered photocurrent has been further enhanced when downward polarizing the PZT thin film. The results reported in this work highlight the superiorities of ferroelectric PZT-based self-powered visible-blind UV photodetectors and provide valuable strategies for the fabrication of high-performance self-powered photodetectors with a simplified device structure in the future.

Significant Modulation of Ferroelectric Photovoltaic Behavior by a Giant Macroscopic Flexoelectric Effect Induced by Strain‐Relaxed Epitaxy

AbstractFlexoelectricity has become an emerging tool to tailor the material properties. The flexoelectric modulation of ferroelectric photovoltaic (FEPV) properties is of particular interest, because it offers an opportunity to boost the photovoltaic efficiency. In most previous studies, the flexoelectric effect is generated by local pressing or macroscopic bending, which, however, results in a local or weak modulation of the FEPV behavior. Here, a significant modulation of the FEPV effect by the strain‐relaxed epitaxy (SRE)‐induced giant macroscopic flexoelectric effect is demonstrated. Using SRE, giant strain gradients (>107 m−1) are generated and tuned in ferroelectric Pb(Zr0.2Ti0.8)O3 epitaxial films. Tuning the giant strain gradient can significantly modify the switchable FEPV properties. Particularly, a photovoltage enhancement as large as ≈0.5 V is achieved. It is suggested that the flexoelectric modulation of FEPV behavior may originate from the flexoelectric polarization‐induced depolarization field. This study highlights the immense application potential of the SRE‐induced flexoelectricity in the engineering of functional thin‐film devices.