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)Pb₂I₇ (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.     

Large‐Scale Synthesis of Freestanding Layer‐Structured PbI2 and MAPbI3 Nanosheets for High‐Performance Photodetection

Recently, due to the possibility of thinning down to the atomic thickness to achieve exotic properties, layered materials have attracted extensive research attention. In particular, PbI₂, a kind of layered material, and its perovskite derivatives, CH₃NH₃PbI₃ (i.e., MAPbI₃), have demonstrated impressive photoresponsivities for efficient photodetection. Herein, the synthesis of large‐scale, high‐density, and freestanding PbI₂ nanosheets is demonstrated by manipulating the microenvironment during physical vapor deposition. In contrast to conventional two‐dimensional (2D) growth along the substrate surface, the essence here is the effective nucleation of microplanes with different angles relative to the in‐plane direction of underlying rough‐surfaced substrates. When configured into photodetectors, the fabricated device exhibits a photoresponsivity of 410 mA W^?1, a detectivity of 3.1 × 10¹¹ Jones, and a fast response with the rise and decay time constants of 86 and 150 ms, respectively, under a wavelength of 405 nm. These PbI₂ nanosheets can also be completely converted into MAPbI₃ materials via chemical vapor deposition with an improved photoresponsivity up to 40 A W^?1. All these performance parameters are comparable to those of state‐of‐the‐art layered‐material‐based photodetectors, revealing the technological potency of these freestanding nanosheets for next‐generation high‐performance optoelectronics.     

2D Lead Dihalides for High‐Performance Ultraviolet Photodetectors and their Detection Mechanism Investigation

2D halide semiconductors, a new family of 2D materials in addition to transition metal dichalcogenides, present ultralow dark current and high light conversion yield, which hold great potential in photoconductive detectors. Herein, a facile aqueous solution method is developed for the preparation of large‐scale 2D lead dihalide nanosheets (PbF_2‐xI_x). High‐performance UV photodetectors are successfully implemented based on 2D PbF_2‐xI_x nanosheets. By modulating the components of halogens, the bandgap of PbF_2‐xI_x nanosheets can be tuned to meet varied detection spectra. The photoresponse dependence on incident power density, wavelength, detection environment, and temperature are systematically studied to investigate their detection mechanism. For PbI₂ photodetectors, they are dominantly driven by a photoconduction mechanism and show a fast response speed and a low noise current density. A high normalized detectivity of 1.5 × 10¹² Jones and an I_ON/I_OFF ratio up to 10³ are reached. On the other hand, PbFI photodetectors demonstrate a photogating mechanism mediated by trap states showing high responsivity. The novel 2D halide materials with wide bandgaps, superior detection performance, and facile synthesis process can enrich the Van der Waals solids family and hold great potential for a wide variety of applications in advanced optoelectronics.     

Low‐Temperature Heteroepitaxy of 2D PbI2/Graphene for Large‐Area Flexible Photodetectors

Heterostructures based on graphene and other 2D atomic crystals exhibit fascinating properties and intriguing potential in flexible optoelectronics, where graphene films function as transparent electrodes and other building blocks are used as photoactive materials. However, large‐scale production of such heterostructures with superior performance is still in early stages. Herein, for the first time, the preparation of a submeter‐sized, vertically stacked heterojunction of lead iodide (PbI₂)/graphene on a flexible polyethylene terephthalate (PET) film by vapor deposition of PbI₂ on graphene/PET substrate at a temperature lower than 200 °C is demonstrated. This film is subsequently used to fabricate bendable graphene/PbI₂/graphene sandwiched photodetectors, which exhibit high responsivity (45 A W^?1 cm^?2), fast response (35 µs rise, 20 µs decay), and high‐resolution imaging capability (1 µm). This study may pave a facile pathway for scalable production of high‐performance flexible devices.     

Self‐Confined Growth of Ultrathin 2D Nonlayered Wide‐Bandgap Semiconductor CuBr Flakes

2D planar structures of nonlayered wide‐bandgap semiconductors enable distinguished electronic properties, desirable short wavelength emission, and facile construction of 2D heterojunction without lattice match. However, the growth of ultrathin 2D nonlayered materials is limited by their strong covalent bonded nature. Herein, the synthesis of ultrathin 2D nonlayered CuBr nanosheets with a thickness of about 0.91 nm and an edge size of 45 µm via a controllable self‐confined chemical vapor deposition method is described. The enhanced spin‐triplet exciton (Z_f, 2.98 eV) luminescence and polarization‐enhanced second‐harmonic generation based on the 2D CuBr flakes demonstrate the potential of short‐wavelength luminescent applications. Solar‐blind and self‐driven ultraviolet (UV) photodetectors based on the as‐synthesized 2D CuBr flakes exhibit a high photoresponsivity of 3.17 A W^?1, an external quantum efficiency of 1126%, and a detectivity (D*) of 1.4 × 10¹¹ Jones, accompanied by a fast rise time of 32 ms and a decay time of 48 ms. The unique nonlayered structure and novel optical properties of the 2D CuBr flakes, together with their controllable growth, make them a highly promising candidate for future applications in short‐wavelength light‐emitting devices, nonlinear optical devices, and UV photodetectors.     

Ultra‐Broadband Flexible Photodetector Based on Topological Crystalline Insulator SnTe with High Responsivity

Topological crystalline insulators (TCIs) are predicted to be a promising candidate material for ultra‐broadband photodetectors ranging from ultraviolet (UV) to terahertz (THz) due to its gapless surface state and narrow bulk bandgap. However, the low responsivity of TCIs‐based photodetectors limits their further applications. In this regard, a high‐performance photodetector based on SnTe, a recently developed TCI, working in a broadband wavelength range from deep UV to mid‐IR with high responsivity is reported. By taking advantage of the strong light absorption and small bandgap of SnTe, photodetectors based on the as‐grown SnTe crystalline nanoflakes as well as specific short channel length achieve a high responsivity (71.11 A W^?1 at 254 nm, 49.03 A W^?1 at 635 nm, 10.91 A W^?1 at 1550 nm, and 4.17 A W^?1 at 4650 nm) and an ultra‐broad spectral response (254–4650 nm) simultaneously. Moreover, for the first time, a durable flexible SnTe photodetector fabricated directly on a polyethylene terephthalate film is demonstrated. These results prove the great potential of TCIs as a promising material for integrated and flexible optoelectronic devices.     

2D Perovskite Sr2Nb3O10 for High-Performance UV Photodetectors

2D perovskites, due to their unique properties and reduced dimension, are promising candidates for future optoelectronic devices. However, the development of stable and nontoxic 2D wide-bandgap perovskites remains a challenge. 2D all-inorganic perovskite Sr₂Nb₃O₁₀ (SNO) nanosheets with thicknesses down to 1.8 nm are synthesized by liquid exfoliation, and for the first time, UV photodetectors (PDs) based on individual few-layer SNO sheets are investigated. The SNO sheet-based PDs exhibit excellent UV detecting performance (narrowband responsivity = 1214 A W⁻¹, external quantum efficiency = 5.6 × 10⁵%, detectivity = 1.4 × 10¹⁴ Jones @270 nm, 1 V bias), and fast response speed (t_rise ≈ 0.4 ms, t_decay ≈ 40 ms), outperforming most reported individual 2D sheet-based UV PDs. Furthermore, the carrier transport properties of SNO and the performance of SNO-based phototransistors are successfully controlled by gate voltage. More intriguingly, the photodetecting performance and carrier transport properties of SNO sheets are dependent on their thickness. In addition, flexible and transparent PDs with high mechanical stability are easily fabricated based on SNO nanosheet film. This work sheds light on the development of high-performance optoelectronics based on low-dimensional wide-bandgap perovskites in the future.     

Low‐Noise and Large‐Linear‐Dynamic‐Range Photodetectors Based on Hybrid‐Perovskite Thin‐Single‐Crystals

Organic–inorganic halide perovskites are promising photodetector materials due to their strong absorption, large carrier mobility, and easily tunable bandgap. Up to now, perovskite photodetectors are mainly based on polycrystalline thin films, which have some undesired properties such as large defective grain boundaries hindering the further improvement of the detector performance. Here, perovskite thin‐single‐crystal (TSC) photodetectors are fabricated with a vertical p–i–n structure. Due to the absence of grain‐boundaries, the trap densities of TSCs are 10–100 folds lower than that of polycrystalline thin films. The photodetectors based on CH₃NH₃PbBr₃ and CH₃NH₃PbI₃ TSCs show low noise of 1–2 fA Hz^?1/2, yielding a high specific detectivity of 1.5 × 10¹³ cm Hz^1/2 W^?1. The absence of grain boundaries reduces charge recombination and enables a linear response under strong light, superior to polycrystalline photodetectors. The CH₃NH₃PbBr₃ photodetectors show a linear response to green light from 0.35 pW cm^?2 to 2.1 W cm^?2, corresponding to a linear dynamic range of 256 dB.     

Large-Scale Ultrathin 2D Wide-Bandgap BiOBr Nanoflakes for Gate-Controlled Deep-Ultraviolet Phototransistors

Ternary two-dimensional (2D) semiconductors with controllable wide bandgap, high ultraviolet (UV) absorption coefficient, and critical tuning freedom degree of stoichiometry variation have a great application prospect for UV detection. However, as-reported ternary 2D semiconductors often possess a bandgap below 3.0 eV, which must be further enlarged to achieve comprehensively improved UV, especially deep-UV (DUV), detection capacity. Herein, sub-one-unit-cell 2D monolayer BiOBr nanoflakes (≈0.57 nm) with a large size of 70 µm are synthesized for high-performance DUV detection due to the large bandgap of 3.69 eV. Phototransistors based on the 2D ultrathin BiOBr nanoflakes deliver remarkable DUV detection performance including ultrahigh photoresponsivity (R_λ, 12739.13 A W⁻¹), ultrahigh external quantum efficiency (EQE, 6.46 × 10⁶%), and excellent detectivity (D*, 8.37 × 10¹² Jones) at 245 nm with a gate voltage (V_g) of 35 V attributed to the photogating effects. The ultrafast response (τ_rise = 102 µs) can be achieved by utilizing photoconduction effects at V_g of −40 V. The combination of photocurrent generation mechanisms for BiOBr-based phototransistors controlled by V_g can pave a way for designing novel 2D optoelectronic materials to achieve optimal device performance.     

Liquid‐Alloy‐Assisted Growth of 2D Ternary Ga2In4S9 toward High‐Performance UV Photodetection

2D ternary systems provide another degree of freedom of tuning physical properties through stoichiometry variation. However, the controllable growth of 2D ternary materials remains a huge challenge that hinders their practical applications. Here, for the first time, by using a gallium/indium liquid alloy as the precursor, the synthesis of high‐quality 2D ternary Ga₂In₄S₉ flakes of only a few atomic layers thick (≈2.4 nm for the thinnest samples) through chemical vapor deposition is realized. Their UV‐light‐sensing applications are explored systematically. Photodetectors based on the Ga₂In₄S₉ flakes display outstanding UV detection ability (R _λ = 111.9 A W^?1, external quantum efficiency = 3.85 × 10⁴%, and D* = 2.25 × 10¹¹ Jones@360 nm) with a fast response speed (τ_ring ≈ 40 ms and τ_decay ≈ 50 ms). In addition, Ga₂In₄S₉‐based phototransistors exhibit a responsivity of ≈10⁴ A W^?1@360 nm above the critical back‐gate bias of ≈0 V. The use of the liquid alloy for synthesizing ultrathin 2D Ga₂In₄S₉ nanostructures may offer great opportunities for designing novel 2D optoelectronic materials to achieve optimal device performance.     

Ultrathin Amorphous Nickel Doped Cobalt Phosphates with Highly Ordered Mesoporous Structures as Efficient Electrocatalyst for Oxygen Evolution Reaction

Herein, the facile preparation of ultrathin (≈3.8 nm in thickness) 2D cobalt phosphate (CoPi) nanoflakes through an oil‐phase method is reported. The obtained nanoflakes are composed of highly ordered mesoporous (≈3.74 nm in diameter) structure and exhibit an amorphous nature. Attractively, when doped with nickel, such 2D mesoporous Ni‐doped CoPi nanoflakes display decent electrocatalytic performances in terms of intrinsic activity, and low kinetic barrier toward the oxygen evolution reaction (OER). Particularly, the optimized 10 at% Ni‐doped CoPi nanoflakes (denoted as Ni10‐CoPi) deliver a low overpotential at 10 mA cm^?2 (320 mV), small Tafel slope (44.5 mV dec^?1), and high stability for OER in 1.0 m KOH solution, which is comparable to the state‐of‐the‐art RuO₂ tested in the same condition (overpotential: 327 mV at 10 mA cm^?2, Tafel slope: 73.7 mV dec^?1). The robust framework coupled with good OER performance enables the 2D mesoporous Ni10‐CoPi nanoflakes to be a promising material for energy conversion applications.     

High‐Performance Photovoltaic Detector Based on MoTe2/MoS2 Van der Waals Heterostructure

Van der Waals heterostructures based on 2D layered materials have received wide attention for their multiple applications in optoelectronic devices, such as solar cells, light‐emitting devices, and photodiodes. In this work, high‐performance photovoltaic photodetectors based on MoTe₂/MoS₂ vertical heterojunctions are demonstrated by exfoliating‐restacking approach. The fundamental electric properties and band structures of the junction are revealed and analyzed. It is shown that this kind of photodetectors can operate under zero bias with high on/off ratio (>10⁵) and ultralow dark current (≈3 pA). Moreover, a fast response time of 60 µs and high photoresponsivity of 46 mA W^?1 are also attained at room temperature. The junctions based on 2D materials are expected to constitute the ultimate functional elements of nanoscale electronic and optoelectronic applications.     

Ultrasensitive and Fast All‐Inorganic Perovskite‐Based Photodetector via Fast Carrier Diffusion

Low trap‐state density, high carrier mobility, and efficient charge carrier collection are key parameters for photodetectors with high sensitivity and fast response time. This study demonstrates a simple solution growth method to prepare CsPbBr₃ microcrystals (MCs) with low trap‐state density. Time‐dependent photoluminescence study with one‐photon excitation (OPE) and two‐photon excitation (TPE) indicates that CsPbBr₃ MCs exhibit fast carrier diffusion with carrier mobility over 100 cm² V^?1 S^?1. Furthermore, CsPbBr₃ MC‐based photodetectors with high charge carriers' collection efficiency are fabricated. Such photodetectors show ultrahigh responsivity (R ) up to 6 × 10⁴ A W^?1 with OPE and high R up to 6 A W^?1 with TPE. The R for OPE is over one order of magnitude higher (the R for TPE is three orders of magnitude higher) than that of previously reported all‐inorganic perovskite‐based photodetectors. Moreover, the photodetectors exhibit fast response time of ≈1 ms, which corresponds to a gain ≈10⁵ and a gain‐ bandwidth product of 10⁸ Hz for OPE (a gain ≈10³ and a gain‐bandwidth product of 10⁶ Hz for TPE).     

Solution‐Processed 3D RGO–MoS2/Pyramid Si Heterojunction for Ultrahigh Detectivity and Ultra‐Broadband Photodetection

Molybdenum disulfide (MoS₂), a typical 2D metal dichalcogenide (2DMD), has exhibited tremendous potential in optoelectronic device applications, especially in photodetection. However, due to the weak light absorption of planar mono‐/multilayers, limited cutoff wavelength edge, and lack of high‐quality junctions, most reported MoS₂‐based photodetectors show undesirable performance. Here, a structurized 3D heterojunction of RGO–MoS₂/pyramid Si is demonstrated via a simple solution‐processing method. Owing to the improved light absorption by the pyramid structure, the narrowed bandgap of the MoS₂ by the imperfect crystallinity, and the enhanced charge separation/transportation by the inserted reduced graphene oxide (RGO), the assembled photodetector exhibits excellent performance in terms of a large responsivity of 21.8 A W^?1, extremely high detectivity up to 3.8 × 10¹⁵ Jones (Jones = cm Hz^1/2 W^?1) and ultrabroad spectrum response ranging from 350 nm (ultraviolet) to 4.3 µm (midwave infrared). These device parameters represent the best results for MoS₂‐based self‐driven photodetectors, and the detectivity value sets a new record for the 2DMD‐based photodetectors reported thus far. Prospectively, the design of novel 3D heterojunction can be extended to other 2DMDs, opening up the opportunities for a host of high‐performance optoelectronic devices.     

Atomically Thin Oxyhalide Solar‐Blind Photodetectors

2D wide‐bandgap semiconductors demonstrate great potential in fabricating solar‐blind ultraviolet (SBUV) photodetectors. However, the low responsivity of 2D solar‐blind photodetectors still limits their practical applications. Here, high‐responsivity solar‐blind photodetectors are achieved based on 2D bismuth oxychloride (BiOCl) flakes. The 2D BiOCl photodetectors exhibit a responsivity up to 35.7 A W^?1 and a specific detectivity of 2.2 × 10¹⁰ Jones under 250 nm illumination with 17.8 µW cm^?2 power density. In particular, the enhanced photodetective performances are demonstrated in BiOCl photodetectors with increasing ambient temperature. Surprisingly, their responsivity can reach 2060 A W^?1 at 450 K under solar‐blind light illumination, maybe owing to the formation of defective BiOCl grains evidenced by in situ transmission electron microscopy. The high responsivity throughout the solar‐blind range indicates that 2D BiOCl is a promising candidate for SBUV detection.     

Gradient Energy Band Driven High‐Performance Self‐Powered Perovskite/CdS Photodetector

Self‐powered photodetectors are highly desired to meet the great demand in applications of sensing, communication, and imaging. Manipulating the carrier separation and recombination is critical to achieve high performance. In this paper, a self‐powered photodetector based on the integrated gradient O‐doped CdS nanorod array and perovskite is presented. Through optimizing the degree of continuous built‐in band bending in the gradient‐O CdS, the photodetector demonstrates a remarkable detectivity of 2.1 × 10¹³ Jones. Under the self‐powered voltage mode, the responsivity can be as high as 0.48 A W^?1, and the rise and decay time are 0.54/2.21 ms. The comprehensive performance is comparable and even better than reported perovskite and other types of self‐powered photodetectors. The improved mechanism reveals that the gradient band bending promotes the photogenerated carrier transfer and hinders the recombination at the interface.     

Ferroelectric Localized Field–Enhanced ZnO Nanosheet Ultraviolet Photodetector with High Sensitivity and Low Dark Current

Zinc oxide (ZnO) nanosheets have demonstrated outstanding electrical and optical properties, which are well suited for ultraviolet (UV) photodetectors. However, they have a high density of intrinsically unfilled traps, and it is difficult to achieve p‐type doping, leading to the poor performance for low light level switching ratio and a high dark current that limit practical applications in UV photodetection. Here, UV photodetectors based on ZnO nanosheets are demonstrated, whose performance is significantly improved by using a ferroelectric localized field. Specifically, the photodetectors have achieved a responsivity of up to 3.8 × 10⁵ A W^?1, a detectivity of 4.4 × 10¹⁵ Jones, and a photocurrent gain up to 1.24 × 10⁶. These device figures of merit are far beyond those of traditional ZnO ultraviolet photodetectors. In addition, the devices' initial dark current can be easily restored after continuous photocurrent measurement by using a positive gate voltage pulse. This study establishes a new approach to produce high‐sensitivity and low‐dark‐current ultraviolet photodetectors and presents a crucial step for further practical applications.     

Ultrasensitive 2D Bi2O2Se Phototransistors on Silicon Substrates

2D materials are considered as intriguing building blocks for next‐generation optoelectronic devices. However, their photoresponse performance still needs to be improved for practical applications. Here, ultrasensitive 2D phototransistors are reported employing chemical vapor deposition (CVD)‐grown 2D Bi₂O₂Se transferred onto silicon substrates with a noncorrosive transfer method. The as‐transferred Bi₂O₂Se preserves high quality in contrast to the serious quality degradation in hydrofluoric‐acid‐assisted transfer. The phototransistors show a responsivity of 3.5 × 10⁴ A W^?1, a photoconductive gain of more than 10⁴, and a time response in the order of sub‐millisecond. With back gating of the silicon substrate, the dark current can be reduced to several pA. This yields an ultrahigh sensitivity with a specific detectivity of 9.0 × 10¹³ Jones, which is one of the highest values among 2D material photodetectors and two orders of magnitude higher than that of other CVD‐grown 2D materials. The high performance of the phototransistor shown here together with the developed unique transfer technique are promising for the development of novel 2D‐material‐based optoelectronic applications as well as integrating with state‐of‐the‐art silicon photonic and electronic technologies.     

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low‐Pressure Vapor‐Assisted Solution Process

The fabrication of multidimensional organometallic halide perovskite via a low‐pressure vapor‐assisted solution process is demonstrated for the first time. Phenyl ethyl‐ammonium iodide (PEAI)‐doped lead iodide (PbI₂) is first spin‐coated onto the substrate and subsequently reacts with methyl‐ammonium iodide (MAI) vapor in a low‐pressure heating oven. The doping ratio of PEAI in MAI‐vapor‐treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV–vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI₂ ratio, which suggests the coexistence of low‐dimensional perovskite (PEA₂MA_n?1Pb_nI_3n+1) with various values of n after vapor reaction. The dimensionality of the as‐fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI₂ ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI‐containing perovskite grain is presumably formed around the MAPbI₃ perovskite grain to benefit MAPbI₃ grain growth. The device employing perovskite with PEAI/PbI₂ = 0.05 achieves a champion power conversion efficiency of 19.10% with an open‐circuit voltage of 1.08 V, a current density of 21.91 mA cm^?2, and a remarkable fill factor of 80.36%.     

Band Structure Engineering of Interfacial Semiconductors Based on Atomically Thin Lead Iodide Crystals

To explore new constituents in two‐dimensional (2D) materials and to combine their best in van der Waals heterostructures is in great demand as being a unique platform to discover new physical phenomena and to design novel functionalities in interface‐based devices. Herein, PbI₂ crystals as thin as a few layers are synthesized, particularly through a facile low‐temperature solution approach with crystals of large size, regular shape, different thicknesses, and high yields. As a prototypical demonstration of band engineering of PbI₂‐based interfacial semiconductors, PbI₂ crystals are assembled with several transition metal dichalcogenide monolayers. The photoluminescence of MoS₂ is enhanced in MoS₂/PbI₂ stacks, while a dramatic photoluminescence quenching of WS₂ and WSe₂ is revealed in WS₂/PbI₂ and WSe₂/PbI₂ stacks. This is attributed to the effective heterojunction formation between PbI₂ and these monolayers; type I band alignment in MoS₂/PbI₂ stacks, where fast‐transferred charge carriers accumulate in MoS₂ with high emission efficiency, results in photoluminescence enhancement, and type II in WS₂/PbI₂ and WSe₂/PbI₂ stacks, with separated electrons and holes suitable for light harvesting, results in photoluminescence quenching. The results demonstrate that MoS₂, WS₂, and WSe₂ monolayers with similar electronic structures show completely distinct light–matter interactions when interfacing with PbI₂, providing unprecedented capabilities to engineer the device performance of 2D heterostructures.