Field-Induced Antiferroelectric-Ferroelectric Transformation in Organometallic Perovskite Displaying Giant Negative Electrocaloric Effect.

Antiferroelectric materials with an electrocaloric effect (ECE) have been developed as promising candidates for solid-state refrigeration. Despite the great advances in positive ECE, reports on negative ECE remain quite scarce because of its elusive physical mechanism. Here, a giant negative ECE (maximum ΔS ∼ -33.3 J kg-1 K-1 with ΔT ∼ -11.7 K) is demonstrated near room temperature in organometallic perovskite, iBA2EA2Pb3I10 (1, where iBA = isobutylammonium and EA = ethylammonium), which is comparable to the greatest ECE effects reported so far. Moreover, the ECE efficiency ΔS/ΔE (∼1.85 J cm kg-1 K-1 kV-1) and ΔT/ΔE (∼0.65 K cm kV-1) are almost 2 orders of magnitude higher than those of classical inorganic ceramic ferroelectrics and organic polymers, such as BaTiO3, SrBi2Ta2O9, Hf1/2Zr1/2O2, and P(VDF-TrFE). As far as we know, this is the first report on negative ECE in organometallic hybrid perovskite ferroelectric. Our experimental measurement combined with the first-principles calculations reveals that electric field-induced antipolar to polar structural transformation results in a large change in dipolar ordering (from 6.5 to 45 µC/cm2 under the ΔE of 18 kV/cm) that is closely related to the entropy change, which plays a key role in generating such giant negative ECE. This discovery of field-induced negative ECE is unprecedented in organometallic perovskite, which sheds light on the exploration of next-generation refrigeration devices with high cooling efficiency.

Renewing Halogen Substitution Strategy for the Rational Design of High-Curie Temperature Metal-Free Molecular Antiferroelectrics.

Metal-free molecular antiferroelectric (AFE) holds a promise for energy storage on account of its unique physical attributes. However, it is challenging to explore high-curie temperature (Tc) molecular AFEs, due to the lack of design strategies regarding the rise of phase transition energy barriers. By renewing the halogen substitution strategy, we have obtained a series of high-Tc molecular AFEs of the halogen-substituted phenethylammonium bromides (x-PEAB, x=H/F/Cl/Br), resembling the binary stator-rotator system. Strikingly, the p-site halogen substitution of PEA+ cationic rotators raises their phase transition energy barrier and greatly enhances Tc up to ~473 K for Br-PEAB, on par with the record-high Tc values for molecular AFEs. As a typical case, the member 4-fluorophenethylammonium bromide (F-PEAB) shows notable AFE properties, including high Tc (~374 K) and large electric polarization (~3.2 µC/cm2). Further, F-PEAB also exhibits a high energy storage efficiency (η) of 83.6 % even around Tc, catching up with other AFE oxides. This renewing halogen substitution strategy in the molecular AFE system provides an effective way to design high-Tc AFEs for energy storage devices.

Building Block-Inspired Hybrid Perovskite Derivatives for Ferroelectric Channel Layers with Gate-Tunable Memory Behavior.

Ferroelectric photovoltaics driven by spontaneous polarization (Ps ) holds a promise for creating the next-generation optoelectronics, spintronics and non-volatile memories. However, photoactive ferroelectrics are quite scarce in single homogeneous phase, owing to the severe Ps fatigue caused by leakage current of photoexcited carriers. Here, through combining inorganic and organic components as building blocks, we constructed a series of ferroelectric semiconductors of 2D hybrid perovskites, (HA)2 (MA)n-1 Pbn Br3n+1 (n=1-5; HA=hexylamine and MA=methylamine). It is intriguing that their Curie temperatures are greatly enhanced by reducing the thickness of inorganic frameworks from MAPbBr3 (n=∞, Tc =239 K) to n=2 (Tc =310 K, ΔT=71 K). Especially, on account of the coupling of room-temperature ferroelectricity (Ps ≈1.5 µC/cm2 ) and photoconductivity, n=3 crystal wafer was integrated as channel field effect transistor that shows excellent a large short-circuit photocurrent ≈19.74 µA/cm2 . Such giant photocurrents can be modulated through manipulating gate voltage in a wide range (±60 V), exhibiting gate-tunable memory behaviors of three current states ("-1/0/1" states). We believe that this work sheds light on further exploration of ferroelectric materials toward new non-volatile memory devices.

Mixing cage cations in 2D metal-halide ferroelectrics enhances the ferro-pyro-phototronic effect for self-driven photopyroelectric detection.

The ferro-pyro-phototronic (FPP) effect, coupling photoexcited pyroelectricity and photovoltaics, paves an effective way to modulate charge-carrier behavior of optoelectronic devices. However, reports of promising FPP-active systems remain quite scarce due to a lack of knowledge on the coupling mechanism. Here, we have successfully enhanced the FPP effect in a series of ferroelectrics, BA2Cs1-xMAxPb2Br7 (BA = butylammonium, MA = methylammonium, 0 ≤ x ≤ 0.34), rationally assembled by mixing cage cations into 2D metal-halide perovskites. Strikingly, chemical alloying of Cs+/MA+ cations leads to the reduction of exciton binding energy, as verified by the x = 0.34 component; this facilitates exciton dissociation into free charge-carriers and boosts photo-activities. The crystal detector thus displays enhanced FPP current at zero bias, almost more than 10 times higher than that of the x = 0 prototype. As an innovative study on the FPP effect, this work affords new insight into the fundamental principle of ferroelectrics and creates a new strategy for self-driven photodetection.

Polarization-Dependent Large Photorefractive Effect In A Wide Bandgap 2D Metal Halide Ferroelectric.

Photorefractive effect of ferroelectrics refers to the light-induced change of refractive index, which is an optical controlling avenue in holographic storage and image processing. For most ferroelectrics, however, the small photorefractive effect (10-5 -10-4 ) hinders their practical application and it is urgent to exploit new photorefractive system. Here, for the first time, strong photorefractive effects are achieved in a 2D metal-halide ferroelectric, [CH3 (CH2 )3 NH3 ]2 (CH3 NH3 )Pb2 Cl7 (1), showing large spontaneous polarization (≈4.1 µC cm-2 ) and wide optical bandgap (≈3.20 eV). Notably, under light irradiation, 1 enables a large variation of refractive indices up to ≈ 1× 10-3 , being one order higher than the existing materials and comparable to the state-of-the-art inorganic ferroelectrics. This intriguing photorefractive behavior involves with the sharp variation of polarization caused by photo-pyroelectricity. As the first report of 2D metal-halide photorefractive ferroelectric, this work sheds light on optical controlling of physical properties in electric-ordered materials.

Visible-Photoactive Perovskite Ferroelectric-Driven Self-Powered Gas Detection.

Chemiresistive sensing has been regarded as the key monitoring technique, while classic oxide gas detection devices always need an external power supply. In contrast, the bulk photovoltage of photoferroelectric materials could provide a controllable power source, holding a bright future in self-powered gas sensing. Herein, we present a new photoferroelectric ([n-pentylaminium]2[ethylammonium]2Pb3I10, 1), which possesses large spontaneous polarization (∼4.8 µC/cm2) and prominent visible-photoactive behaviors. Emphatically, driven by the bulk photovoltaic effect, 1 enables excellent self-powered sensing responses for NO2 at room temperature, including extremely fast response/recovery speeds (0.15/0.16 min) and high sensitivity (0.03 ppm-1). Such figures of merit are superior to those of typical inorganic systems (e.g., ZnO) using an external power supply. Theoretical calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements confirm the great selectivity of 1 for NO2. As far as we know, this is the first realization of ferroelectricity-driven self-powered gas detection. Our work sheds light on the self-powered sensing systems and provides a promising way to broaden the functionalities of photoferroelectrics.

Improper High-Tc Perovskite Ferroelectric with Dielectric Bistability Enables Broadband Ultraviolet-to-Infrared Photopyroelectric Effects.

The photopyroelectric effect in ferroelectrics has shown great potential for application in infrared detection and imaging. One particular subclass is broadband with dielectric bistability, which allows for large pyroelectric figures-of-merit (FOMs). Herein, an improper high-Tc perovskite ferroelectric, (IA)2 (EA)2 Pb3 Cl10 (1, where IA is isoamylammonium and EA is ethylammonium) is presented, in which spontaneous polarization (Ps ) stems from the dynamic ordering of organic cations and the tilting of distorted PbCl6 octahedra. Notably, 1 displays unusual dielectric bistability with small variations in the temperature-dependent dielectric constants near Tc  = 392 K; this bistable attribute endows large pyroelectric FOMs with peak voltage efficiency (FV  = 1.7×10-2  cm2 µC-1 ) and sensitivity (FD  = 3.9×10-4 Pa-1/2 ). These FV and FD parameters, beyond those of their proper counterparts, make 1 a promising candidate for infrared photodetection. As expected, the broadband photopyroelectric effects observed in 1 covered the ultraviolet to infrared-II spectral region (266-1950 nm). Such Ps -directed photoactivities overcome the optical bandgap limitation and allow for wide-wave photodetection. As an innovative study on improper ferroelectricity, light is shaded here on the targeted engineering of new electrically ordered candidate materials for smart optoelectronic devices.

Acquiring Bulk Anomalous Photovoltaic Effect in Single Crystals of a Lead-Free Double Perovskite with Aromatic and Alkali Mixed-Cations.

The bulk anomalous photovoltaic (BAPV) effect of acentric materials refers to a distinct concept from traditional semiconductor-based devices, of which the above-bandgap photovoltage hints at a promise for solar-energy conversion. However, it is still a challenge to exploit new BAPV-active systems due to the lacking of knowledge on the structural origin of this concept. BAPV effects in single crystals of a 2D lead-free double perovskite, (BBA)2 CsAgBiBr7 (1, BBA = 4-bromobenzylammonium), tailored by mixing aromatic and alkali cations in the confined architecture to form electric polarization are acquired here. Strikingly, BAPV effects manifested by above-bandgap photovoltage (VOC ) show unique attributes of directional anisotropy and positive dependence on electrode spacing. The driving source stems from orientations of the polar aromatic spacer and Cs+ ion drift, being different from the known built-in asymmetry photovoltaic heterojunctions. As the first demonstration of the BAPV effect in the double perovskites, the results will enrich the family of environmentally green BAPV-active candidates and further facilitate their new optoelectronic application.

Ferroelectric perovskite-type films with robust in-plane polarization toward efficient room-temperature chemiresistive sensing.

Ferroelectric materials have become key components for versatile device applications, and their thin films are highly desirable for integrating the miniaturized devices. Despite substantial endeavors, it is still challenging to achieve effective chemiresistive sensing in the ferroelectric films. Here, for the first time, we have exploited ferroelectric thin films of 2D hybrid perovskite BA2EA2Pb3I10 (1), to fabricate the high-performance chemiresistor gas sensors. The spin-coated films of 1 exhibit high orientation and good crystallinity, thus preserving robust in-plane spontaneous polarization (P s ∼2.0 µC/cm2) and low electric coercivity. Notably, such ferroelectric film-based sensors after electric poling enable the dramatic room-temperature sensing responses to NO2 gas, including high sensitivity (0.05 ppm-1), extremely low detection limit (1 ppm) and fast responding rate (∼6 s). Besides, the chemiresistive responses are remarkably enhanced by threefold (up to 320%) through electric poling. It is proposed that this behavior closely involves with strong in-plane ferroelectric polarization of 1 that generates a built-in electric field inhibiting the recombination of charge carriers. As far as we know, this ferroelectric-based film chemiresisor is one of the best room-temperature sensors for NO2 gas among all the existing candidate materials. These findings highlight great potential of ferroelectrics toward effective chemiresistive performances, and also establish a bright direction to explore their future device applications.

X-ray-Induced Pyroelectric Effect in a Perovskite Ferroelectric Drives Low Detection Limit Self-Powered Responses.

The light-induced pyroelectric effect (LPE) has shown a great promise in the application of optoelectronic devices, especially for self-powered detection and imaging. However, it is quite challenging and scarce to achieve LPE in the X-ray region. For the first time, we report X-ray LPE in a single-phase ferroelectric of (NPA)2(EA)2Pb3Br10 (1, NPA = neopentylamine, EA = ethylamine), adopting a two-dimensional trilayered perovskite motif, which has a large spontaneous polarization of ∼3.7 µC/cm2. Its ferroelectricity allows for significant LPE in the wavelength range of ordinary visible light. Strikingly, the X-ray LPE is observed in 1, which endows remarkable self-powered X-ray responses at 0 bias, including sensitivity up to 225 µC Gy-1 cm-2 and a low detection limit of ∼83.4 nGy s-1, being almost 66 times lower than the requirement for medical diagnostics (∼5.5 µGy s-1). This work not only develops a new mode for X-ray detection but also provides valuable insights for future photoelectric device application.

A room-temperature antiferroelectric in hybrid perovskite enables highly efficient energy storage at low electric fields.

Molecular antiferroelectrics (AFEs) have taken a booming position in the miniaturization of energy storage devices due to their low critical electric fields. However, regarding intrinsic competitions between dipolar interaction and steric hindrance, it is a challenge to exploit room-temperature molecular AFEs with high energy storage efficiency. Here, we present a new 2D hybrid perovskite-type AFE, (i-BA)2(FA)Pb2Br7 (1), which shows ultrahigh energy storage efficiencies at room temperature. Most strikingly, the typical double P-E hysteresis loops afford an ultrahigh storage efficiency up to ∼91% at low critical electric fields (E cr = 41 kV cm-1); this E cr value is much lower than those of state-of-the-art AFE oxides, revealing the potential of 1 for miniaturized energy-storage devices. In terms of the energy storage mechanism, the dynamic ordering and antiparallel reorientation of organic cations trigger its AFE-type phase transition at 303 K, thus giving a large spontaneous electric polarization of ∼3.7 µC cm-2, while the increasement of steric hindrance of the organic branched-chain i-BA+ spacer cations stabilizes its antipolar sublattices. To the best of our knowledge, this exploration of achieving ultrahigh energy storage efficiency at such a low critical electric field is unprecedented in the AFE family, which paves a pathway for miniaturized energy storage applications.

Soft Multiaxial Molecular Ferroelectric Thin Films with Self-Powered Broadband Photodetection.

Molecular ferroelectric films (MFFs) offer a good platform for miniaturized electronic devices, which are inseparable from their multiaxial nature. Despite great studies, soft MFFs with broadband photo-electroactivity still remain a huge blank as the photoexcited leakage current will severely deteriorate ferroelectricity, hindering their optoelectronic applications. Here, we constructed the multiaxial MFF of HA2EA2Pb3I10 (1, where EA = ethylammonium and HA = n-hexylammonium) in 2D multilayered perovskites. Eight equivalent polarization directions were observed in 1, as verified by its symmetry breaking (i.e., 4/mmmFm species), which is the maximum among 2D multilayered perovskites and even more than that of classic ceramic BaTiO3. Specially, spin-coated flexible MFFs of 1 are approximately orientated parallel to layered perovskite frameworks, exhibiting in-plane spontaneous polarization (Ps = 1.8 µC/cm2) and broadband absorption (∼1.83 eV). In addition, self-powered broadband detection (∼0.55 µA/cm2 at 637 nm illumination) was achieved on the soft films, revealing their potential for flexible and wearable electronic devices. Our result sheds light on the design of flexible photoelectronic devices and provides an effective way to expand the applications of 2D molecular ferroelectric materials.

Record high-Tc and large practical utilization level of electric polarization in metal-free molecular antiferroelectric solid solutions.

Metal-free antiferroelectric materials are holding a promise for energy storage application, owing to their unique merits of wearability, environmental friendliness, and structure tunability. Despite receiving great interests, metal-free antiferroelectrics are quite limited and it is a challenge to acquire new soft antiferroelectric candidates. Here, we have successfully exploited binary CMBrxI1-x and CMBrxCl1-x solid solution as single crystals (0 ≤ x ≤ 1, where CM is cyclohexylmethylammonium). A molecule-level modification can effectively enhance Curie temperature. Emphatically, the binary CM-chloride salt shows the highest antiferroelectric-to-paraelectric Curie temperature of ~453 K among the known molecular antiferroelectrics. Its characteristic double electrical hysteresis loops provide a large electric polarization up to ~11.4 µC/cm2, which endows notable energy storage behaviors. To our best knowledge, this work provides an effective solid-solution methodology to the targeted design of new metal-free antiferroelectric candidates toward biocompatible energy storage devices.

Comprehensive Analysis of Prognostic Value and Immune Infiltration of IGFBP Family Members in Glioblastoma.

Glioblastoma (GBM) is the most common primary malignant brain tumor in adults. The insulin-like growth factor-binding protein (IGFBP) family is involved in tumorigenesis and the development of multiple cancers. However, little is known about the prognostic value and regulatory mechanisms of IGFBPs in GBM. Oncomine, Gene Expression Profiling Interactive Analysis, PrognoScan, cBioPortal, LinkedOmics, TIMER, and TISIDB were used to analyze the differential expression, prognostic value, genetic alteration, biological function, and immune cell infiltration of IGFBPs in GBM. We observed that IGFBP1, IGFBP2, IGFBP3, IGFBP4, and IGFBP5 mRNA expression was significantly upregulated in patients with GBM, whereas IGFBP6 was downregulated; this difference in mRNA expression was statistically insignificant. Subsequent investigations showed that IGFBP4 and IGFBP6 mRNA levels were significantly associated with overall survival in patients with GBM. Functional Gene Ontology Annotation and Kyoto Encyclopedia of Genes and Genomes pathway enrichment analysis revealed that genes coexpressed with IGFBP4 and IGFBP6 were mainly enriched in immune-related pathways. These results were validated using the TIMER and TSMIDB databases. This study demonstrated that the IGFBP family has prognostic value in patients with GBM. IGFBP4 and IGFBP6 are two members of the IGFBP family that had the highest prognostic value; thus, they have the potential to serve as survival predictors and immunotherapeutic targets in GBM.

Incorporating an Aromatic Cationic Spacer to Assemble 2D Polar Perovskite Crystals toward Self-Powered Detection of Quite Weak Polarized Light.

Two-dimensional (2D) hybrid perovskites with intrinsic attributes of structural and optical anisotropy are holding a bright promise for polarization-sensitive photodetection. However, studies on self-powered detection to quite weak polarized light remain scarce in this 2D family. By incorporating an aromatic spacer into the 3D cubic prototype, we have successfully assembled a new 2D hybrid perovskite with a polar motif, (FPEA)2(MA)Pb2I7 (FMPI, where FPEA is 4-fluorophenethylammonium and MA is methylammonium). Its unique 2D quantum-well structure allows optical absorption dichroism with a large ratio of ∼3.15, and the natural polarity results in a notable bulk photovoltaic effect. Further, centimeter-size crystals (10 × 10 × 3 mm3) of FMPI were facilely obtained by the temperature cooling method, and its crystal-based detectors enable excellent self-powered detection of quite weak polarized light, showing a notable polarization-sensitive ratio (∼1.5), extremely low detection limit (∼100 nW/cm2), and antifatigued stability. The alloyed aromatic cationic spacers facilitate the polarity and enhanced phase stability. This study paves a way for further exploration of new 2D perovskite candidates toward optoelectronic device applications.

Anisotropy in a 2D Perovskite Ferroelectric Drives Self-Powered Polarization-Sensitive Photoresponse for Ultraviolet Solar-Blind Polarized-Light Detection.

Polarized-light detection in the deep ultraviolet solar-blind region is indispensable for optoelectronic applications. 2D hybrid perovskite ferroelectrics with inherent anisotropy and bulk photovoltaic effect (BPVE) have become a robust candidate in this portfolio. We here report a wide band-gap 2D perovskite ferroelectric, (isobutylammonium)2 (methylamium)Pb2 Cl7 (1), in which the BPVE behaves as self-driving source for solar-blind ultraviolet polarized-light detection. It exhibits a large dichroism ratio (≈15.7) and superior BPVE-directed photocurrent (≈3.6 µA cm-2 , under 266 nm). These attributes facilitate excellent self-powered polarized-light detection of high on/off contrast (≈103 ) and polarization ratio (≈2.5), beyond those of inorganic oxides (e.g., ZnO, 1.47; GaN, 1.38). This study highlights potential of 2D perovskite ferroelectrics for new optoelectronic application.

Tailoring Interlayered Spacers of Two-Dimensional Cesium-Based Perovskite Ferroelectrics toward Exceptional Ferro-Pyro-Phototronic Effects.

Ferro-pyro-phototronic (FPP) effect is a triple coupling of ferroelectricity, light-induced pyroelectricity, and photo-excitation, which holds a bright promise for next-generation modern optoelectronic devices. However, except for few oxides (e.g., BaTiO3 ), new FPP-active candidates remain extremely scarce due to the knowledge lacking on the underlying role of three coupling components. By tailoring the interlayered spacers, the authors present a series of 2D cesium-based perovskite ferroelectrics, (A')2 CsPb2 Br7 (where A'-site cation is organic spacer), showing remarkable FPP-active properties. As expected, the dynamic ordering and reorientation of spacers along with atomic displacement of Cs+ in the perovskite cavity lead to their ferroelectric polarizations. Particularly, exceptional FPP properties are created through this cooperation; the most FPP-active candidate (n-hexylammonium)2 CsPb2 Br7 endows a giant contrast up to 1500% for photopyroelectric current to photovoltaic signal. This figure-of-merit is far beyond most inorganic oxide counterparts, such as ≈110% for BaTiO3 . Further, the electric switching and controlling of FPP directions confirm a crucial role of ferroelectric polarization to this coupling effect. To the authors' best knowledge, this is the first study on an FPP-active candidate of 2D hybrid perovskites, which affords a new avenue to design ferroelectrics with targeted physical properties and forward their potentials to smart optoelectronic device application.

2D Hybrid perovskite incorporating cage-confined secondary ammonium cations toward effective photodetection.

By confining the secondary dimethylammonium (DMA) cation in a distorted perovskite cavity, we assembled a new 2D Ruddlesden-Popper metal halide perovskite of (i-BA)2(DMA)Pb2Br7 (i-BA = n-isobutylammonium), in which the DMA cation templates its inorganic perovskite framework and the quantum-well motif renders a fascinating photoresponse. Crystal-based planar arrays exhibit effective photodetection behaviors, including a notable detectivity (∼5.6 × 1012 Jones), a high responsivity (∼1.25 A W-1) and a large switching ratio (∼1.5 × 103). These properties result from its low dark current restricted to the hopping barrier of the insulated organic bilayer and a strong in-plane photoresponse correlated with the perovskite network. This work throws light on the targeted exploration of photosensitive candidates in the family of organic-inorganic hybrid perovskites, as well as high-performance devices.

A Metal-Free Molecular Antiferroelectric Material Showing High Phase Transition Temperatures and Large Electrocaloric Effects.

Antiferroelectric (AFE) materials, featuring an antiparallel alignment of electric dipoles in the adjacent sublattices, are keeping a great promise toward solid-state refrigeration applications on account of their electrocaloric (EC) effects. Although extensive studies have been performed on inorganic oxide counterparts (e.g., PbZrO3 and AgNbO3), metal-free molecular AFE alternatives with the above-room-temperature EC activities are quite scarce but urgently demanded in terms of environmental issues. Herein, we present a new metal-free molecular AFE, cyclohexylmethylammonium bromide (CMB), which exhibits the unusual antiferroelectric-ferroelectric-paraelectric phase transitions around 364 and 368 K upon heating. The phase transition temperatures are much higher than the majority of known molecular AFE materials. The practical utilization level of electric polarization (∼6 µC/cm2) is clearly evidenced by the typical double polarization-electric field hysteresis loops. Strikingly, large positive and negative EC responses with the temperature changes (ΔT) of 4.2 and -3 K are achieved under an electric field of 20 kV/cm. The origin of its antiferroelectricity and EC properties is elucidated by the antipolar reorientation of cations along with displacement of bromine anions, being distinct from the known mechanism of inorganic oxides. Such intriguing AFE behaviors, including large polarization and EC effects, reveal great potentials of CMB for the solid-state refrigeration. This study sheds light on further exploration of new AFE candidates toward environmentally friendly solid-state cooling devices.

A reduced-dimensional polar hybrid perovskite for self-powered broad-spectrum photodetection.

Polar hybrid perovskites have been explored for self-powered photodetection benefitting from prominent transport of photo-induced carriers and the bulk photovoltaic effect (BPVE). However, these self-powered photodetection ranges are relatively narrow depending on their intrinsic wide bandgaps (>2.08 eV), and the realization of broad-spectrum self-powered photodetection is still a difficult task. Herein, we successfully obtained a polar multilayered perovskite, (I-BA)2(MA)2Pb3I10 (IMP, MA+ = methylammonium and I-BA+ = 4-iodobutylammonium), via rational dimension reduction of CH3NH3PbI3. It features the narrowest bandgap of 1.71 eV in a BPV material. As a consequence, the integration of narrow bandgap and BPVE causes the self-powered photodetection to extend to 724 nm for IMP, and a repeatable photovoltaic current reaching 1.0 µA cm-2 is acquired with a high "on/off" ratio of ∼103 and photodetectivity (∼109 Jones) at zero bias. This innovative research provides a foothold for adjusting the physical properties of hybrid perovskites and will expand their potential for self-powered broad-spectrum detection.