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

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(39), P. 18062 - 18068

Published: Sept. 23, 2022

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

Language: Английский

---

Chirality Inducing Polar Photovoltage in a 2D Lead-Free Double Perovskite toward Self-Powered X-ray Detection

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(6), P. 2809 - 2816

Published: May 31, 2023

Lead-free halide double perovskites (HDPs) have sparked broad interest in developing "green" photodetectors; however, self-powered X-ray detectors this family remain elusive. Here, by exploiting the chirality-induced polar photovoltaic effect a chiral-polar 2D HDP, (R-MPA)4AgBiI8 (1, R-MPA = R-β-methylphenethylammonium), we successfully realized detection. The significant spontaneous electric polarization 1 gives it large photovoltage of 0.36 V, which drives separation and transport X-ray-generated carriers, thus acquiring capability Consequently, based on high-quality single crystals exhibit high sensitivity 46.3 μC Gy–1 cm–2 an ultralow detection limit 85 nGy s–1 at zero bias. can be further increased to 949.6 50 V bias, outperforming all current HDP detectors. Our work is first demonstrate single-phase lead-free HDPs, enlightening future design radiation

Language: Английский

---

Inch‐Size Single Crystals of Lead‐Free Chiral Perovskites with Bulk Photovoltaic Effect for Stable Self‐Driven X‐Ray Detection

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(36)

Published: May 8, 2023

Abstract Lead halide perovskites have made great advance in direct X‐ray detection, however the presence of toxic lead and requirement high working voltages severely limit their applicability operational stability. Thus, exploring “green” lead‐free hybrid capable detecting X‐rays at zero bias is crucial but remains toughly challenging. Here, utilizing chiral R / S ‐1‐phenylpropylamine ( ‐PPA) cations, a pair 0D chiral‐polar perovskites, 2 BiI 5 1 ) are constructed. Their intrinsic spontaneous electric polarization induces large bulk photovoltage 0.63 V, which acts as driving force to separate transport photogenerated carriers, thus endowing them with capability self‐driven detection. Consequently, detectors low detection 270 nGy s −1 successfully constructed based on high‐quality, inch‐sized single crystals . Notably, they show suppressed baseline drift under mode, exhibiting superior This study realizes single‐phase perovskite by exploiting photovoltaic effect, sheds light future explorations toward radiation performance.

Language: Английский

---

Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para-Substituent Effects

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Two-dimensional (2D) organic–inorganic hybrid metal halides (OIMHs), characterized by noncentrosymmetric structures arising from the incorporation of chiral organic molecules that break inversion symmetry, have attracted significant attention. Particularly, chiral-polar 2D OIMHs offer a unique platform for multifunctional applications, as coexistence chirality and polarity enables simultaneous manifestation distinct properties such nonlinear optical (NLO) effects, circular dichroism (CD), ferroelectricity. In this study, we report first synthesis hafnium (Hf)-based OIMHs, achieved through strategic para-substituents on benzene ring components. By tuning substituents, successfully modulate crystal structures, resulting in both chiral-nonpolar systems. Our analysis structural properties, supported density functional theory calculations, demonstrates these materials can be systematically tuned, enabling adjustable band gaps CD UV range (200–280 nm). Notably, halogen substitution at para-position layer produces tunable ranging 4.33 to 4.48 eV, widest reported date OIMHs. Furthermore, exhibit enhanced NLO including remarkable 3.3-fold increase second-harmonic generation intensity compounds compared their counterparts. These findings position Hf-based promising candidates UV-region devices self-driven circularly polarized light detectors, offering new opportunities designing optoelectronic harnessing interplay between polarity.

Language: Английский

---

Emerging Opportunities in Lead-Free and Lead–Tin Perovskites for Environmentally Viable Photodetector Applications

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(9), P. 3404 - 3426

Published: April 24, 2023

In modern society, photodetectors (PDs) have permeated virtually all areas of human life, from home appliances to space exploration. This versatility generates a high demand for photodetectors. It is attributed their ability detect signals spanning broad spectrum wavelengths while possessing advantageous mechanical properties such as light weight, flexibility, and low cost. Metal halide perovskites (PSKs) recently emerged effective because detection range extends the visible near-infrared (NIR) through adjustment chemical composition. addition having notable successes in photovoltaic applications, gained attention photodetector applications due superior optoelectronic properties. Incorporating toxic Pb offsets desirability performance main component perovskites. issue was addressed by replacing with relatively nontoxic Sn retain unique To promote continued advancement reduced toxicity, we provide comprehensive overview current research on Sn–Pb mixed perovskites, emphasizing crystal structures, properties, synthesis, modification methods. We then highlight exemplary detailed introductions. Simultaneously, challenges respective solutions development are discussed this Review. Review concludes novel outlook future directions Sn-rich perovskite potential candidates enhancing signal technologies. explain how enhancement enables comparable that commercially available crystalline Si III–V

Language: Английский

---

Toward Efficient Two‐Photon Circularly Polarized Light Detection through Cooperative Strategies in Chiral Quasi‐2D Perovskites

Advanced Science, Journal Year: 2023, Volume and Issue: 10(9)

Published: Jan. 22, 2023

Abstract Organic–inorganic hybrid perovskites carry unique semiconducting properties and advanced flexible crystal structures. These characteristics of organic–inorganic create a promising candidacy for circularly polarized light (CPL) detection. However, CPL detections based on chiral are limited to UV visible wavelengths. The natural quantum well structures layered generate strong light–matter interactions. This makes it possible achieve near‐infrared (NIR) detection via two‐photon absorption in the sub‐wavelength region. In this study, cooperative strategies dimension increase mixed spacer cations used obtain pair multilayered (R‐ β ‐MPA)EA 2 Pb Br 7 (S‐ (MPA = methylphenethylammonium EA ethylammonium). distinctive bi‐cations interlayer inorganic skeletons provide enhanced photoconduction. Moreover, superior photoconduction leads prominent NIR response with responsivity up 8.1 × 10 −5 A W −1 . It is anticipated that work can serve as benchmark fabrication optimization efficient by simple chemical design.

Language: Английский

---

Integrating Achiral and Chiral Organic Ligands in Zero‐Dimensional Hybrid Metal Halides to Boost Circularly Polarized Luminescence

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 24, 2023

Chiral zero-dimensional hybrid metal halides (0D HMHs) could combine excellent optical properties and chirality, making them promising for circularly polarized luminescence (CPL). However, chiral 0D HMHs with efficient CPL have been rarely reported. Here, we propose an strategy to achieve simultaneously high photoluminescence quantum yield (PLQY) large dissymmetry factor (glum ), by integrating achiral ligands into HMHs. Specifically, three pairs of indium-antimony chlorides are synthesized combing guanidine types methylbenzylammonium-based derivatives as the organic cations. These exhibit near-unity PLQY glum values up around ±1×10-2 . The ligand is not only essential crystallize these PLQYs, but also greatly enhances chirality induction from inorganic units in Furthermore, choice different can modify strength hydrogen bonding interactions HMHs, maximize their values. Overall, this study provides a robust way realize expanding applications chiroptical fields.

Language: Английский

---

Recent progress in layered metal halide perovskites for solar cells, photodetectors, and field-effect transistors

Nanoscale, Journal Year: 2023, Volume and Issue: 15(9), P. 4219 - 4235

Published: Jan. 1, 2023

Metal halide perovskite materials demonstrate immense potential for photovoltaic and electronic applications. In particular, two-dimensional (2D) layered metal perovskites have advantages over their 3D counterparts in optoelectronic applications due to outstanding stability, structural flexibility with a tunable bandgap, confinement effect. This review article first analyzes the crystallography of different 2D phases [the Ruddlesden-Popper (RP) phase, Dion-Jacobson (DJ) alternating cations interlayer space (ACI) phase] at molecular level compares common properties, such as out-of-plane conductivity, crucial vertical devices. paper then critically reviews recent development devices, namely solar cells, photodetectors field effect transistors, based on points out limitations compared counterparts. It also identifies important application-specific future research directions devices providing comprehensive view guiding new this field.

Language: Английский

---

Chirality Versus Symmetry: Electron's Spin Selectivity in Nonpolar Chiral Lead–Bromide Perovskites

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(51)

Published: Aug. 1, 2023

Abstract In the last decade, chirality‐induced spin selectivity (CISS), spin‐selective electron transport through chiral molecules, has been described in a large range of materials, from insulators to superconductors. Because more experimental studies are desired for theoretical understanding CISS effect, metal‐halide semiconductors may contribute field thanks their chiroptical and spintronic properties. this regard, work uses new organic cations S ‐HP1A R (HP1A = 2‐hydroxy‐propyl‐1‐ammonium) prepare 2D halide perovskites (HPs) which crystallize enantiomorphic space groups P 4 3 2 1 2, respectively. The fourfold symmetry induces antiferroelectricity along stacking axis which, combined incomplete Rashba‐like splitting each individual polar layer, results rare textures band structure. As revealed by magnetic conductive‐probe atomic force microscopy (AFM) measurements, these materials show effect with partial polarization (SP; ±40–45%). This is efficient enough drive chiro‐spintronic device as demonstrated fabrication valve devices magnetoresistance (MR) responses up 250 K. Therefore, stable lead–bromide HP not only represent interesting candidates applications but also reveal importance symmetry‐breaking topology selectivity.

Language: Английский

---

Discovering New Type of Lead‐Free Cluster‐Based Hybrid Double Perovskite Derivatives with Chiral Optical Activities and Low X‐Ray Detection Limit

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(26)

Published: March 24, 2023

Abstract 2D chiral hybrid perovskites have recently emerged as outstanding semiconductor materials. However, most of the reported limited structural types and contain high levels toxic lead, which severely hinders their further applications. Herein, by using a mixed‐cation strategy, an unprecedented type lead‐free cluster‐based double perovskite derivatives are successfully obtained, [( R / S ‐PPA) 4 (IPA) 6 Ag 2 Bi I 24 ]·2H O ( 1‐R 1‐S ), n ‐BA) 2‐R 2‐S ) ‐PPA= –1‐phenylpropylamine; IPA=isopentylamine; ‐BA= ‐butylamine). Their inorganic skeletons linked binuclear {Bi 10 } infinite chain {Ag 14 ∞ , in bismuth clusters multiple coordination modes (e.g., tetrahedral AgI octahedral introduced into system for first time. This introduction induces distortion layer, may facilitate transfer chirality from cations achiral skeletons. Further, circular dichroism measurements circularly polarized light detection confirm inherent optical activities. In addition, exhibits ultralow X‐ray limit 129.5 nGy s −1 is 42‐fold lower than that demands regular medical diagnosis (5.5 µGy ). study provides pathway to construct novel derivatives.

Language: Английский

---