Three-Dimensional Polar Perovskites for Highly Sensitive Self-Driven X-Ray Detection.

Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) have achieved tremendous success in direct X-ray detection due to their high absorption coefficient and excellent carrier transport. However, owing to the centrosymmetry of classic 3D structures, these reported X-ray detectors mostly require external electrical fields to run, resulting in bulky overall circuitry, high energy consumption, and operational instability. Herein, we first report the unprecedented radiation photovoltage in 3D OIHP for efficient self-driven X-ray detection. Specifically, the 3D polar OIHP MhyPbBr3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47 V) and large mobility-lifetime product (1.1×10-3  cm2 V-1 ) under X-ray irradiation. Strikingly, these excellent physical characteristics endow 1 with sensitive self-driven X-ray detection performance, showing a considerable sensitivity of 220 µC Gy-1 cm-2 , which surpasses those of most self-driven X-ray detectors. This work first explores highly sensitive self-driven X-ray detection in 3D polar OIHPs, shedding light on future practical applications.

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.

Circularly Polarized Light-Dependent Pyro-Phototronic Effect from 2D Chiral-Polar Double Perovskites.

Chiral hybrid perovskites combine the advantages of chiral materials and halide perovskites, offering an ideal platform for the design of circularly polarized light (CPL) detectors. The pyro-phototronic effect, as a special mechanism of the photoexcited pyroelectric signal, can significantly improve the performance of photodetectors, whereas it remains a great challenge to achieve pyroelectricity-based CPL detection. In this work, the chiroptical phenomena and the pyro-phototronic effect are combined in chiral-polar perovskites to achieve unprecedented pyroelectric-based CPL detection. Two novel two-dimensional (2D) lead-free chiral-polar double perovskites, S/R-[(4-aminophenyl)ethylamine]2AgBiI8·0.5H2O, are successfully designed and synthesized by introducing chiral organic ligands into metal halide frameworks. Strikingly, the photoresponse is substantially boosted with the support of the pyro-phototronic effect, showing an increased pyro-phototronic current that is 40 times greater than the photovoltaic current. Furthermore, the pyroelectric-based detector possesses excellent CPL detection capacity to distinguish different polarization states of CPL photons, which achieve an impressive glph of up to 0.27 at zero bias. This study provides a brand new process for CPL detection by utilizing the pyro-phototronic effect in chiral-polar perovskites, which opens a new avenue for chiral materials in optoelectronic applications.

Realization of Passive X-Ray Detection with a Low Detection Limit in Dion-Jacobson Halide Hybrid Perovskite.

Halide hybrid perovskites are a kind of intriguing contenders for X-ray detection, and their low detection limits (LoDs) have played a crucial part in X-ray safety inspection and medical examination. However, there is still a significant challenge in manufacturing perovskite X-ray detectors with low LoDs. Herein, attributed to the bulk photovoltaic effect (BPVE) of a Dion-Jacobson (DJ) type 2D halide hybrid perovskite polar structure (3-methylaminopropylamine)PbBr4 (1), self-powered X-ray detection with low detection limit is successfully realized. Specifically, the crystal-based detector of 1 exhibits a low dark current at zero bias, which reduces the noise current (0.34 pA), leading to a low detection limit (58.3 nGyair s-1 ) which is two orders of magnitude lower than that of under external voltage bias. The combination of BPVE and LoDs of halide hybrid perovskite provides an efficient strategy to achieve passive X-ray detection with low doses.

Chain-to-Layer Dimensionality Engineering of Chiral Hybrid Perovskites to Realize Passive Highly Circular-Polarization-Sensitive Photodetection.

Chiral hybrid perovskites (CHPs), aggregating chirality and favorable semiconducting properties in one, have taken a prominent position in direct circularly polarized light detection (CPL). However, passive high circular polarization sensitivity (gres) photodetection in CHPs is still elusive and challenging. Benefitting from efficient control and turning of carrier transport of CHPs by dimensional engineering, here, we unprecedentedly proposed a chain-to-layer dimensionality engineering to realize high-gres passive photodetection. Two novel 2D layered CHPs (R/S-PPA)EAPbBr4 (2R/2S) (PPA = 1-phenylpropylamine, EA = ethylammonium) are successfully synthesized by alloying an EA cation with small steric hindrance into the chained CHPs (R/S-PPA)PbBr3 (1R/1S). Particularly, compared with the neglectable photoresponse in 1R, the obtained 2R by chain-to-layer dimensionality engineering gives rise to an excellent photoconductivity and robust polar photovoltage effect (PPE) with a giant open-circuit voltage of 2.5 V. Furthermore, such PPE promotes realizing an impressive gres in 2R up to 0.42 at zero bias because of the independent separation of photoexcited carriers, which is the highest value among the reported layered chiral perovskites. This work paves the way for the vigorous development of higher dimensional CHPs and will reveal their applications in the field of passive high-gres CPL detection.

Robust Spin-Dependent Anisotropy of Circularly Polarized Light Detection from Achiral Layered Hybrid Perovskite Ferroelectric Crystals.

Circularly polarized light (CPL) detection has sparked overwhelming research interest for its widespread chiroptoelectronic and spintronic applications. Ferroelectric materials, especially emerging layered hybrid perovskite ferroelectrics, exhibiting striking bulk photovoltaic effect (BPVE) present significant possibilities for CPL detection by a distinctive working concept. Herein, for the first time, we demonstrate the realization of robust angular anisotropy of CPL detection in a new layered hybrid perovskite ferroelectric crystal (CPA)2FAPb2Br7 (1, CPA is chloropropylammonium, FA is formamidinium), which crystallized in an optically active achiral polar point group. Benefiting from the notable spontaneous polarization (5.1 µC/cm2) and excellent semiconducting characteristics, single crystals of 1 exhibit remarkable BPVE under light illumination, with a high current on/off switching ratio (ca. 103). More intriguingly, driven by the angular carrier drift originating from spin-dependent BPVE in optically active ferroelectrics, 1 displays highly sensitive self-powered CPL detection performance, showing a robust angular anisotropy factor up to 0.98, which is far more than those achieved by material intrinsic chirality. This work provides an unprecedented approach for realizing highly sensitive CPL detection, which sheds light on the further design of optically active ferroelectrics for chiral photonic applications.

Multilayered Alternating-Cations-Intercalation Chiral Hybrid Perovskites with High Circular Polarization Sensitivity.

Multilayered chiral hybrid perovskites are highly desired for highly-sensitive circularly polarized light (CPL) detection rooted in their efficient charge transport and strong chiroptical activity. However, designing multilayered chiral hybrid perovskites remains a huge challenge. Here, through pairing achiral ethylamine (EA)-chiral arylamine in the interlayer space, multilayered chiral alternating cations intercalation-type (ACI) hybrid perovskites (R-/S-PPA) EA2 Pb2 Br7 (PPA = 1-phenylpropylamine) are successfully obtained. Significantly, perovskitizer EA extends the thickness of the quantum well and alternating space cation EA greatly alleviates in-plane tilting distortions of adjacent metal halide octahedra, providing fast channels for in-plane carrier transport. Consequently, single-crystal photodetectors of (R-/S-PPA) EA2 Pb2 Br7 exhibit high circular polarization sensitivity with a large anisotropy factor of 0.3, which falls around the highest value among the layered hybrid perovskites. In addition, a fast responding rate (τr )of 308 µs and a high CPL-detectivity of 8 × 1012 Jones are also presented. This work opens up a new perspective to design multilayered chiral hybrid perovskites for high-sensitive CPL detection.

Localized Lattice Expansion of FAPbBr3 to Design a 3D Hybrid Perovskite for Sensitive Near-Infrared Photodetection.

A mixed-cation 3D lead bromide hybrid perovskite (NMDAP)2 FAPb4 Br13 (1, NMDAP2+ = N-methyl-1,3-diaminopropanium, FA+ = formamidinium) is tailored by incorporating the large NMDAP2+ cation with the small FA+ ion into 3D FAPbBr3 . Structurally, the small FA+ ions occupy the prototypical cavities formed by distorted corner-sharing PbBr6 octahedra as in FAPbBr3 , while the bulky NMDAP2+ ions are confined to the expanded lattice which is defined by a new structural motif composed of eight corner-sharing PbBr6 octahedra and four edge-sharing octahedra. This localized lattice expansion from FAPbBr3 creates a new branch of the intriguing 3D hybrid perovskite family, breaking the limits of the conventional Goldschmidt tolerance factor rule. Moreover, a high two-photon absorption (2AP) coefficient of 60.8 cm MW-1 was demonstrated to near-infrared (NIR) 800 nm illumination, enabling sensitive NIR photoresponses with large on/off ratio (≈104 ) as well as favorable stability.

In Situ Epitaxial Growth of Centimeter-Sized Lead-Free (BA)2CsAgBiBr7/Cs2AgBiBr6 Heterocrystals for Self-Driven X-ray Detection.

Halide perovskite heterocrystals, composed of distinct perovskite single crystals, have generated great interest for both fundamental research and applied device designs. One of the key advantages of using such a heterocrystal is its built-in electric potential, which enhances charge transport and suppresses the noise in the solid-state devices. On the basis of this strategy, high-performance optoelectronic devices (e.g., X-ray detectors) have been successfully demonstrated. However, the toxicity of metal cations (Pb) in those reported heterocrystals hinders their wider applications. Thus, developing lead-free halide perovskite heterocrystals is significant but remains highly challenging. Here, we report a solution-processed in situ heteroepitaxial approach that enables us to create the first lead-free halide perovskite heterocrystal, (BA)2CsAgBiBr7/Cs2AgBiBr6(BA = n-butylammonium), with dimensions of up to 10 × 7 × 6 mm3. The as-grown heterocrystals have high crystalline quality and present near atomically sharp interfaces. More excitingly, the (BA)2CsAgBiBr7/Cs2AgBiBr6 heterogeneous integration allows the formation of a built-in electric potential in the junction, which triggers spontaneous charge separation/transport. Consequently, X-ray detectors using the heterocrystals can operate in a self-driven mode and exhibit an impressive sensitivity (206 µC Gy-1 cm-2) superior to that of the pristine Cs2AgBiBr6 crystal detectors, an ultralow dark current, and operational stability. Our findings provide the first demonstration of lead-free halide perovskite heterocrystals and may open up opportunities for a host of sustainable and miniaturized perovskite optoelectronic devices.

Bromine-Substitution-Induced High-Tc Two-Dimensional Bilayered Perovskite Photoferroelectric.

High-Curie-temperature (Tc) ferroelectrics have exhibited broad applications in optoelectronic devices. Recently, two-dimensional multilayered perovskite ferroelectrics with excellent photoelectric attributes are attracting increasing interest as new systems of photoferroelectrics. However, the effective tuning of the Tc value of a multilayered perovskite photoferroelectric system still remains a huge challenge. Here, by a halogen substitution strategy to introduce bromine atoms on n-propylamine cations, the hybrid perovskite photoferroelectric (3-bromopropylaminium)2(formamidinium)Pb2Br7 (BFPB) with a high Tc value (348.5 K) was obtained. It is notable that BFPB adopts a two-dimensional bilayered inorganic framework, with tight linking to the organic cation by C-Br···Br-Pb halogen···halogen interactions and N-H···Br hydrogen bonds. Intriguingly, in comparison with the prototypical compound (n-propylaminium)2(formamidinium)Pb2Br7, a remarkable augmentation of 85.2 K in the resulting Tc value of BFPB is clearly observed, which further broadens the temperature range of its application. In combination with the remarkable ferroelectric and semiconducting attributes, the reversible bulk photovoltaic effect was realized in single crystals of BFPB. This finding can not only enhance the hybrid perovskite ferroelectric family but also further promote the photoelectric application of ferroelectrics.

Monolayer-to-Multilayer Dimensionality Reconstruction in a Hybrid Perovskite for Exploring the Bulk Photovoltaic Effect Enables Passive X-ray Detection.

Halide hybrid perovskites are attracting considerable attention as highly promising candidates for directly sensing X-ray radiation, but it is challenging to realize passive X-ray detection without an external power supply. However, the bulk photovoltaic effect (BPVE) in ferroelectrics promotes the independent separation of photoexcited carriers. Herein, by dimensionality reconstruction of a pure-two-dimensional (P-2D) monolayered perovskite (CH3 OC3 H9 N)2 PbBr4 , we obtained a quasi-two-dimensional (Q-2D) ferroelectric (CH3 OC3 H9 N)2 CsPb2 Br7 . Converting P-2D into Q-2D perovskite stimulates a significant BPVE associated with robust ferroelectricity, as well as an enhanced mobility lifetime product. These features show the potential of the first passive X-ray detector based on ferroelectrics with an impressive sensitivity up to 410 µC Gy-1 cm-2 at zero bias, which is even superior to the value of the state-of-the-art α-Se detector operated at relatively high bias.

A Potential Sn-Based Hybrid Perovskite Ferroelectric Semiconductor.

Ferroelectric semiconductors, combining semiconduction, spontaneous polarization, and photoinduced excitation, show great promise to enhance the performance of solar cells, pressure sensors, and photodetectors. Particularly, organic-inorganic lead halide perovskite ferroelectrics have been explored for their prominent carrier transport properties and structural tunability. However, a high concentration of toxic Pb is a stumbling block for their further application. Here, we present a lead-free hybrid perovskite semiconductor, (C4H9NH3)2(NH3CH3)2Sn3Br10 (1), which exhibits a large spontaneous polarization of 11.76 µC cm-2 at room temperature. Significantly, 1 presents a spontaneous polar ordering transition, similar to the better-known perovskite ferroelectrics, and exhibits ferroelectric phase transition behaviors. To our best knowledge, 1 is the first example of a Sn-based hybrid perovskite semiconductor featuring ferroelectric performance. Mechanistic studies reveal that such ferroelectricity can be attributable to the synergistic effects of ordering of organic cations and stereochemically active lone-pair electrons inducing distortion of inorganic octahedra. This work provides an effective way to explore "green" ferroelectric semiconductors with potentially enhanced energy conversion efficiency.

Trilayered Lead Chloride Perovskite Ferroelectric Affording Self-Powered Visible-Blind Ultraviolet Photodetection with Large Zero-Bias Photocurrent.

Perovskite ferroelectrics, in which the spontaneous polarization (Ps) is conducive to the separation of photoexcited charge carriers, have shown great potential for self-powered photodetection. Nevertheless, such self-powered ferroelectric photodetectors are mostly dominated by traditional inorganic oxides and exhibit relatively small zero-bias photocurrent, which limit their further application. Herein, we present a wide-bandgap 2D trilayered lead chloride hybrid perovskite ferroelectric, EA4Pb3Cl10 (1, EA = ethylammonium), which shows a notable Ps of ∼4.5 µC/cm2 and a high Curie temperature (415 K) beyond that of BaTiO3 (393 K). Significantly, benefiting from the wide bandgap of 3.39 eV, a self-powered visible-blind ultraviolet (UV) photodetector has been successfully realized, with a zero-bias photocurrent as high as 18.6 µA/cm2, which is nearly 2 orders of magnitude larger than those of mostly conventional inorganic ferroelectrics. As a pioneering study, this work offers an efficient approach for exploring wide-bandgap perovskite ferroelectrics and will excavate their application in the field of self-powered visible-blind UV photodetection.

Ferroelectricity-Driven Self-Powered Ultraviolet Photodetection with Strong Polarization Sensitivity in a Two-Dimensional Halide Hybrid Perovskite.

Polarization-sensitive ultraviolet (UV) photodetection is highly indispensable in military and civilian applications and has been demonstrated with various wide-band photodetectors. However, it still remains elusive to achieve the self-powered devices, which can be operated in the absence of external bias. Herein, for the first time, ferroelectricity-driven self-powered photodetection towards polarized UV light was successfully demonstrated in a 2D wide-band gap hybrid ferroelectric (BPA)2 PbBr4 (BPA=3-bromopropylammonium) (1). We found that the prominent spontaneous polarization in 1 results in a bulk photovoltaic effect (BPVE) of 0.85 V, that independently drives photoexcited carriers separation and transport and thus supports self-powered ability. This self-powered detector shows strong polarization sensitivity to linearly polarized UV illumination with a polarization ratio up to 6.8, which is superior to that of previously reported UV-polarized photodetectors (ZnO, GaN, and GeS2 ).

Exploiting the Bulk Photovoltaic Effect in a 2D Trilayered Hybrid Ferroelectric for Highly Sensitive Polarized Light Detection.

Polarized light detection is attracting increasing attention for its wide applications ranging from optical switches to high-resolution photodetectors. Two-dimensional (2D) hybrid perovskite-type ferroelectrics combining inherent light polarization dependence of bulk photovoltaic effect (BPVE) with excellent semiconducting performance present significant possibilities. Now, the BPVE-driven highly sensitive polarized light detection in a 2D trilayered hybrid perovskite ferroelectric, (allyammonium)2 (ethylammonium)2 Pb3 Br10 (1), is presented. It shows a superior BPVE with near-band gap photovoltage of ca. 2.5 V and high on/off switching ratio of current (ca. 104 ). Driven by the superior BPVE, 1 exhibits highly sensitive polarized light detection with a polarization ratio as high as ca. 15, which is far more beyond than those of structural anisotropy-based monocomponent devices. This is the first realization of BPVE-driven polarized light detection in hybrid perovskite ferroelectrics.

An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric with Directionally Tunable Photovoltaic Effects.

Multiaxial molecular ferroelectrics, in which multiple-directional switching of spontaneous polarization creates diverse properties, have shown many intriguing advantages, making them indispensable complements to conventional inorganic oxides. Despite recent blooming advances, multiaxial molecular ferroelectric with bulk photovoltaic effects still remains a huge blank. Herein, we report a biaxial lead halide ferroelectric, EA4Pb3Br10 (1, EA = ethylammonium), which adopts the unique trilayered perovskite motif with a high Curie temperature of ∼384 K. Particularly, for 1, the distinct symmetry breaking with 4/ mmmF mm2 species leads to the emergence of four equivalent polarization directions in the ferroelectric phase. Based on its biaxial nature, the bulk photovoltaic effect of 1 can be facilely tuned between such multiple directions through electric poling. As far as we know, this is the first report on biaxial hybrid perovskite ferroelectric showing directionally tunable photovoltaic activity. This work provides an avenue to control the bulk physical properties of multiaxial molecular ferroelectrics, and highlights their potential for further applications in the field of smart devices.

Tailored Synthesis of an Unprecedented Pb-Mn Heterometallic Halide Hybrid with Enhanced Emission.

Organic-inorganic lead halide hybrids have attracted extensive interest in solid-state lighting, due to their superior color tunability and low-cost solution processing. However, the relatively low photoluminescence quantum efficiency (PLQE) is a common issue for most bulk lead halide hybrids. Inspired by the intriguing luminescence properties of heterometallic complexes, we rationally developed an unprecedented two-dimensional (2D) Pb-Mn heterometallic halide hybrid, (C5H14N2)2Pb4MnCl14 (2), through a precisely tailored synthetic approach based on (C5H14N2)2Pb5Cl14 (1). Intriguingly, 2 features a unique 2D heterometallic halide layer configuration, in which the strong quantum confinement facilitates efficient energy transfer from bound excitons to d-states of Mn2+, resulting in highly sensitized Mn2+emission. The PLQE of 2 is up to 32%, considerably higher than that of pristine 1 (less than 1%). Moreover, 2 presents significant environmental and thermal stability, benefiting from its cluster feature. To our best knowledge, this is the first example of construction of a Pb-Mn heterometallic halide hybrid with bulk highly efficient red emission. This work provides a way to enhance the PLQE of lead halide hybrids via sensitization in rationally designed heterometallic halide hybrids.

Discovery of an Above-Room-Temperature Antiferroelectric in Two-Dimensional Hybrid Perovskite.

Antiferroelectric materials have been regarded as a promising candidate for electronic energy storage devices, due to their natural double polarization versus electric field ( P- E) hysteresis loops. Currently, two-dimensional organic-inorganic hybrid perovskites with structural diversity and tunability, have received blooming interests, whereas above-room-temperature antiferroelectrics are still unreported in this perovskite system. Herein, for the first time, we successfully acquire a two-dimensional Ruddlesden-Popper hybrid perovskite antiferroelectric, ((CH3)2CHCH2NH3)2CsPb2Br7 (1), which shows an above-room-temperature Curie temperature at 353 K, trigging by the synergistic dynamic motion of inorganic Cs atoms and organic isobutylammonium cations. Intriguingly, the antiferroelectricity of 1 existing over a wide temperature range of 298-353 K are revealed by the distinct double P- E hysteresis loops. Besides, 1 possesses remarkable energy storage efficiency up to 69%, comparable to those of some reported inorganic antiferroelectric ceramics, promoting 1 potential application in energy storage devices. This work provides an avenue to construct novel antiferroelectric materials for high-performance electronic device applications.

Highly Oriented Thin Films of 2D Ruddlesden-Popper Hybrid Perovskite toward Superfast Response Photodetectors.

2D hybrid perovskites have shown great promise in the photodetection field, due to their intriguing attributes stemming from unique structural architectures. However, the great majority of detectors based on this 2D system possess a relatively low response speed (≈ms), making it extremely urgent to develop new candidates for superfast photodetection. Here, a new organic-inorganic hybrid perovskite, (PA)2 (FA)Pb2 I7 (EFA, where PA is n-pentylaminium and FA is formamidine), which features the 2D Ruddlesden-Popper type perovskite framework that is composed of the corner-sharing PbI6 octahedra is reported. Significantly, photodetectors fabricated on highly oriented thin films, which exhibit a perfect orientation parallel to 2D inorganic perovskite layers, exhibit a superfast response time up to ≈2.54 ns. To the best of the knowledge, this figure-of-merit catches up with that of the top-ranking commercial materials, and sets a new record for 2D hybrid perovskite photodetectors. Moreover, extremely high photodetectivity (≈1.73 × 1014 Jones, under an incident power intensity of ≈46 µW cm-2 ), considerable switching ratios (>103 ), and low dark current (≈10 pA) are also achieved in the detector, indicating its great potential for high-efficiency photodetection. These results shed light on the possibilities to explore new 2D candidates for assembling future high-performance optoelectronic devices.

[C5 H12 N]SnCl3 : A Tin Halide Organic-Inorganic Hybrid as an Above-Room-Temperature Solid-State Nonlinear Optical Switch.

Nonlinear optical (NLO) switches driven by a solid-state structural phase transition have attracted extensive attention; however, above-room-temperature solid-state NLO switch materials are still sparse. Herein, we report an above-room-temperature tin halide organic-inorganic hybrid quadratic NLO switchable material, N-methylpyrrolidinium trichloride stannite ([C5 H12 N]SnCl3 , MPSC). The MPSC crystal exhibits a phase-matchable NLO property that is 1.1 times that of KH2 PO4 (KDP) and NLO switching behavior, changing from a high second harmonic generation (SHG) response to a low SHG response at 383 K, thereby demonstrating its prospective applications in the field of nonlinear optics. Variable-temperature crystal structural analysis combined with theoretical calculations revealed that the large NLO response stems from the inorganic SnCl3 moiety, whereas the high-performance NLO switching properties mainly originate from the order/disorder transformation of the N-methylpyrrolidinium. This work provides a new approach to designing and exploring new high-performance quadratic NLO switches involving tin halide organic-inorganic hybrids.